WO2012118160A1 - Adhesive composition, laminated body, and solar battery module - Google Patents

Adhesive composition, laminated body, and solar battery module Download PDF

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Publication number
WO2012118160A1
WO2012118160A1 PCT/JP2012/055278 JP2012055278W WO2012118160A1 WO 2012118160 A1 WO2012118160 A1 WO 2012118160A1 JP 2012055278 W JP2012055278 W JP 2012055278W WO 2012118160 A1 WO2012118160 A1 WO 2012118160A1
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WIPO (PCT)
Prior art keywords
adhesive composition
polyurethane resin
adhesive
film
mass
Prior art date
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PCT/JP2012/055278
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French (fr)
Japanese (ja)
Inventor
有賀　広志
小田　康一
達也 宮嶋
Original Assignee
旭硝子株式会社
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Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to EP12751824.9A priority Critical patent/EP2682443A1/en
Priority to JP2013502404A priority patent/JPWO2012118160A1/en
Priority to KR1020137021201A priority patent/KR20140014130A/en
Priority to CN2012800088083A priority patent/CN103380186A/en
Publication of WO2012118160A1 publication Critical patent/WO2012118160A1/en
Priority to US14/016,590 priority patent/US20140000702A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]

Definitions

  • the present invention relates to an adhesive composition, a laminate, and a solar cell module.
  • Fluoropolymer film has excellent weather resistance, and can maintain good transparency and mechanical strength even after outdoor exposure for 10 years, for example. Therefore, for example, it is used as a protective film laminated on the surface of various printed materials and display materials. In recent years, it has been used as a surface material for solar cell modules in place of glass.
  • the surface material that uses a fluororesin film is an ethylene-vinyl acetate copolymer (EVA) sheet that protects solar cells and a polyethylene sheet that has improved adhesiveness, without using an adhesive. It is manufactured by a laminating method in which a fluororesin film is directly thermocompression bonded at a certain temperature. However, this surface material is inferior in water vapor barrier property compared to a surface material using glass because the water vapor barrier property (water vapor barrier property) of the fluororesin film is insufficient.
  • EVA ethylene-vinyl acetate copolymer
  • a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a polyethylene (PE) film, or the like as a water vapor barrier film on a fluororesin film as a surface material.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PE polyethylene
  • the adhesive composition when laminating the PET film with the fluororesin film has ultraviolet absorptivity, for example, the use of an adhesive composition containing an ultraviolet absorber and EVA (patent) References 1 and 2).
  • a back material for a solar cell at least an inorganic oxide layer, an adhesive layer, and an electrical insulating layer are sequentially laminated on at least one surface of a transparent fluororesin film, and the adhesion is performed in order to improve weather resistance.
  • a back material in which an organic ultraviolet absorber is contained in an amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of resin solids constituting the adhesive layer in the layer has been proposed (see Patent Document 3).
  • an adhesive composition containing a polyurethane adhesive and a triazole organic ultraviolet absorber is used for the adhesive layer of the back material.
  • These adhesive compositions are required to maintain a stable adhesion state over a long period of time and to maintain a high ultraviolet absorption function.
  • it is important to be able to reduce discoloration and decrease in adhesion in accelerated weathering tests of at least 1000 hours and constant temperature and humidity tests at 85 ° C. and a relative humidity of 85%. It is.
  • Patent Document 4 discloses a building material base material in which a tetrafluoroethylene copolymer resin film and a vinyl chloride resin film are laminated via at least an ultraviolet absorption acrylic resin layer (Patent Document 4). reference).
  • the ultraviolet absorbing acrylic resin a copolymer of a reactive benzophenone compound or a reactive benzotriazole compound having an ultraviolet absorbing ability and an acrylic monomer having a polymerizable unsaturated group is used.
  • Patent Document 5 discloses a surface protective film in which a coating layer mainly composed of the ultraviolet-absorbing acrylic resin and the heat-adhesive resin is provided on a resin film mainly composed of an ethylene-tetrafluoroethylene copolymer. Is disclosed.
  • Japanese Patent No. 3978912 Japanese Patent No. 3530595 Japanese Unexamined Patent Publication No. 2008-270647 Japanese Patent Laid-Open No. 10-205056 Japanese Patent No. 3718901
  • An object of the present invention is to provide an adhesive composition that can form an adhesive layer that can maintain a high adhesion and an excellent ultraviolet absorption function over a long period of time as an adhesive composition that can be used for solar cell applications and the like.
  • an adhesive layer formed of the adhesive composition is laminated on a substrate made of a resin film such as a fluororesin film, and has high adhesion and excellent ultraviolet absorption function over a long period of time. It aims at providing the laminated body which can be sustained, and the solar cell module using this laminated body.
  • A polyurethane resin
  • B curing agent
  • C triazine-based ultraviolet absorber
  • D light stabilizer
  • the triazine-based ultraviolet absorber (C) includes a hydroxyphenyltriazine-based ultraviolet absorber.
  • the hydroxyphenyltriazine ultraviolet absorber is 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5 -The adhesive composition according to [3], comprising triazine.
  • Any of [1] to [5], wherein the equivalent ratio NCO / OH between the hydroxyl group of the polyurethane resin (A) and the isocyanate group of the curing agent (B) is 1.0 to 5.0.
  • the adhesive composition of the present invention can form an adhesive layer that can maintain a high adhesion and an excellent ultraviolet absorbing function over a long period of time as an adhesive composition that can be used for solar cell applications and the like.
  • the laminate of the present invention has an adhesive layer formed of the adhesive composition of the present invention laminated on a substrate made of a resin film such as a fluororesin film, it has high adhesion and excellent ultraviolet absorption. The function can be maintained for a long time.
  • the solar cell module of this invention has the laminated body of this invention, it can maintain the outstanding weather resistance over a long period of time.
  • the adhesive composition of the present invention comprises a polyurethane resin (A) using a polycarbonate polyol (a1) as a raw material, a curing agent (B), a triazine-based ultraviolet absorber (C) (hereinafter simply referred to as “UV absorber (C ) "And a light stabilizer (D).
  • the polyurethane resin (A) is a polyurethane resin using the polycarbonate polyol (a1) as a raw material.
  • the polyurethane resin (A) is obtained by reacting a polycarbonate polyol (a1), an alkylene diol chain extender (a2) (hereinafter sometimes referred to as “chain extender (a2)”) and an organic diisocyanate (a3).
  • chain extender (a2) hereinafter sometimes referred to as “chain extender (a2)”
  • chain extender (a2) an organic diisocyanate
  • Polyurethane resin (A1) or polyurethane resin (A2) obtained by reacting polycarbonate polyol (a1) and organic diisocyanate (a3) is preferred.
  • Examples of the polycarbonate polyol (a1) include a polycarbonate polyol obtained by a reaction between a diol and a short-chain dialkyl carbonate.
  • Examples of the short-chain dialkyl carbonate include dialkyl carbonates having an alkyl group having 1 to 4 carbon atoms such as dimethyl carbonate and diethyl carbonate.
  • the short-chain dialkyl carbonate used for forming the polycarbonate polyol (a1) may be only one kind or two or more kinds.
  • the alkyl group which polycarbonate polyol (a1) has may have a linear structure or a branched structure.
  • a diol having a branched alkyl side chain is preferable from the viewpoint of improving the adhesive strength.
  • the diol having a branched alkyl side chain include 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2- And butyl-2-ethyl-1,3-propanediol.
  • diol having a branched alkyl side chain does not have a branched alkyl side chain such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
  • Diols may be used.
  • the diol used for forming the polycarbonate polyol (a1) may be only one type or two or more types.
  • the number of moles of units derived from the diol having a branched alkyl side chain relative to the total number of moles of units derived from the diol in the polycarbonate polyol (a1) is preferably 20 mol% or more, and more preferably 30 mol% or more. If the number of moles of the unit derived from the diol having a branched alkyl side chain is not less than the lower limit value, the adhesive strength is improved.
  • the weight average molecular weight of the polycarbonate polyol (a1) is preferably 400 to 8,000, more preferably 700 to 5,000. If the said weight average molecular weight is more than a lower limit, the solubility with respect to a practical synthesis solvent will become more favorable. On the other hand, if the weight average molecular weight is not more than the upper limit value, sufficient adhesive strength can be easily obtained and the practicality is improved.
  • the hydroxyl value of the polycarbonate polyol (a1) is preferably 14 to 280 mg / KOH, more preferably 22 to 160 mg / KOH.
  • the hydroxyl value of the polycarbonate polyol (a1) is at least the lower limit value, the crosslinking reaction is sufficiently facilitated, the molecular weight distribution of the product is narrowed, and the hydrolysis resistance after crosslinking becomes better.
  • the hydroxyl value of the polycarbonate polyol (a1) is not more than the upper limit value, a high molecular weight product is hardly generated in the crosslinking reaction, and an adhesive layer having flexibility to follow the fluorine film is easily formed.
  • Examples of the chain extender (a2) include the same diols as those exemplified as the diol forming the polycarbonate polyol (a1). From the viewpoint of improving the adhesive strength, a diol having a branched alkyl side chain is preferable.
  • the molecular weight of the chain extender (a2) is preferably 62 to 400.
  • preferred examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3- Mention may be made of methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol.
  • the number of moles of units derived from the diol having a branched alkyl side chain relative to the total number of moles of units derived from the diol in the chain extender (a2) is preferably 5 mol% or more, and more preferably 20 mol% or more. If the number of moles of units derived from the diol having a branched alkyl side chain is not less than the lower limit value, the adhesive strength is improved.
  • organic diisocyanate (a3) examples include the following.
  • Aromatic diisocyanates (diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, and prepolymers of said aromatic diisocyanate and low molecular glycols, etc.), Aliphatic diisocyanates (1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, and the above-mentioned aliphatic diisocyanates and low molecular glycols such as ethylene glycol and propylene glycol Prepolymer), Alicyclic diisocyanates (isophorone diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, methylcyclohexylene diisocyanate, isopropylidene dicyclohexyl-4
  • organic diisocyanate (a3) aliphatic compounds such as hydrogenated 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc. from the viewpoint of excellent weather resistance among the above-mentioned ones. Alicyclic diisocyanates are preferred.
  • the polyurethane resin (A) preferably has a hydroxyl group at the terminal.
  • the equivalent ratio (NCO / OH) of the hydroxyl group of the polycarbonate polyol (a1) and the chain extender (a2) to the isocyanate group of the organic diisocyanate (a3) is 0.7 to 0.99. It is preferable that it is 0.8 to 0.97.
  • the NCO / OH is at least the lower limit value, the adhesive strength and heat resistance are improved.
  • the NCO / OH is not more than the upper limit value, it is easy to obtain a main agent having a sufficient amount of hydroxyl groups at the terminals.
  • the amount of the chain extender (a2) used is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate polyol (a1). If the usage-amount of chain extender (a2) is more than a lower limit, adhesive strength will improve. If the usage-amount of a chain extender (a2) is below an upper limit, the solubility with respect to the synthetic solvent mentioned later will improve.
  • the equivalent ratio NCO / OH between the hydroxyl group of the polycarbonate polyol (a1) and the isocyanate group of the organic diisocyanate (a3) is preferably 0.7 to 0.99.
  • the NCO / OH is at least the lower limit value, the adhesive strength and heat resistance are improved.
  • the NCO / OH is not more than the upper limit value, it is easy to obtain a main agent having a sufficient amount of hydroxyl groups at the terminals.
  • the hydroxyl value of the polyurethane resin (A) is preferably 3 to 20 mg / KOH, more preferably 5 to 10 mg / KOH. If the hydroxyl value of the polyurethane resin (A) is at least the lower limit, a crosslinking reaction with an isocyanate used as a two-component curing agent can be expected. When the hydroxyl value of the polyurethane resin (A) is not more than the upper limit value, the crosslinking reaction with the isocyanate used as the two-component curing agent is likely to occur uniformly in a relatively short time.
  • the weight average molecular weight of the polyurethane resin (A) is preferably 4,000 to 50,000, and more preferably 8,000 to 15,000. If the weight average molecular weight of a polyurethane resin (A) is more than a lower limit, adhesive strength will improve. If the weight average molecular weight of a polyurethane resin (A) is below an upper limit, the solubility with respect to the synthetic solvent mentioned later will improve, and workability will become more favorable.
  • the reaction of the polycarbonate polyol (a1), the chain extender (a2), and the organic diisocyanate (a3) may be performed without a solvent or in a synthetic solvent that does not react with an isocyanate group. Moreover, you may react in presence of a catalyst as needed.
  • the reaction temperature is preferably 60 to 150 ° C.
  • the reaction time is preferably 2 to 15 hours.
  • Examples of the synthetic solvent that does not react with the isocyanate group include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; toluene and xylene Aromatic hydrocarbons such as methylene chloride, ethylene chloride, and the like; dimethyl sulfoxide, dimethyl sulfoamide, and the like. These synthetic solvents can also be used as a dilution solvent after synthesis of the main agent.
  • a polyurethane resin (A) may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the curing agent (B) include polyisocyanate.
  • Examples of the polyisocyanate include an adduct of a diisocyanate and a polyol exemplified in the organic diisocyanate (a3), an isocyanurate of a diisocyanate exemplified in the organic diisocyanate (a3), a burette, and an allophanate in one molecule. Those having two or more isocyanate groups are exemplified.
  • an adduct obtained by adding 3 mol of diisocyanate to 1 mol of trimethylolpropane, a burette obtained by reacting 1 mol of water with 3 mol of diisocyanate, or 3 mol of Examples thereof include polyfunctional organic polyisocyanates such as isocyanurate obtained by polymerization of diisocyanate.
  • an isocyanurate body containing an isocyanurate ring structure and having an isocyanate group content of 10% by mass to 28% by mass is preferable.
  • a nurate body of isophorone diisocyanate (IPDI) and / or hexamethylene diisocyanate (HDI) is particularly preferable.
  • the curing agent (B) may be a blocked isocyanate in which an isocyanate group is blocked.
  • the isocyanate group can be blocked with epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OX), methyl isobutyl ketone oxime (MIBK-OX), pyraridine, triazine (TA) and the like.
  • E-CAP epsilon caprolactam
  • MEK-OX methyl ethyl ketone oxime
  • MIBK-OX methyl isobutyl ketone oxime
  • TA triazine
  • curing agent (B) may be used individually by 1 type, and may use 2 or more types together.
  • the ultraviolet absorber (C) is a triazine-based ultraviolet absorber.
  • a ultraviolet absorber (C) a well-known triazine derivative can be used as a ultraviolet absorber, and it can obtain from a commercial item.
  • the ultraviolet absorber (C) a hydroxyphenyltriazine-based ultraviolet absorber is preferable.
  • a hydroxyphenyl triazine type ultraviolet absorber the following ultraviolet absorber is mentioned, for example.
  • 2- (4,6-bis (2,4-dimethylphenyl) -1 The following compounds obtained by reaction of 3,5-triazin-2-yl) -5-hydroxyphenyl with [(alkyloxy) methyl] oxirane having an alkyl group having 10 to 16 carbon atoms, mainly 12 to 13 carbon atoms (3).) Etc.
  • preferable ultraviolet absorber (C) other than a hydroxyphenyl triazine type ultraviolet absorber.
  • UV absorber (C) 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) is excellent in heat resistance and hardly volatilizes. ) -1,3,5-triazine is preferred.
  • a ultraviolet absorber (C) may be used individually by 1 type, and may use 2 or more types together.
  • Light stabilizer (D) As a light stabilizer (D), a well-known thing can be used and it can obtain from a commercial item.
  • a hindered amine light stabilizer or a hindered phenol light stabilizer is preferable, and a hindered amine light stabilizer is more preferable.
  • Examples of the hindered amine light stabilizer include the following.
  • hindered phenol light stabilizer examples include pentaerythritol-tetrakis- [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] (the following compound (6)). Then, trade name “IRGANOX 1010” manufactured by Ciba Japan Co., Ltd.) and the like can be mentioned.
  • the amount is preferably 0.1 to 4.0 parts by weight, and more preferably 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the solid content of the two-component reactive polyurethane adhesive of the present invention. More preferred.
  • the adhesive composition of the present invention is in addition to the polyurethane resin (A), the curing agent (B), the ultraviolet absorber (C) and the light stabilizer (D) as long as the effects of the present invention are not hindered. If necessary, other components other than the polyurethane resin (A), the curing agent (B), the ultraviolet absorber (C) and the light stabilizer (D) may be contained.
  • Another component includes an adhesion promoter. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, and epoxy resins. Of these, a silane coupling agent is preferable.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ (aminoethyl) - ⁇ .
  • Aminosilanes such as aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Epoxy silanes such as glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, - mercaptopropyltrimethoxysilane, and the like.
  • epoxy silanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane are
  • Examples of other components include resins other than the polyurethane resin (A), UV absorbers other than the UV absorber (C), reaction catalysts, antifoaming agents, leveling agents, and antioxidants. .
  • resins other than the polyurethane resin (A) include resins other than the polyurethane resin (A), UV absorbers other than the UV absorber (C), reaction catalysts, antifoaming agents, leveling agents, and antioxidants.
  • resin which the adhesive composition of this invention contains is only a polyurethane resin (A).
  • the ultraviolet absorber which the adhesive composition of this invention contains is only a ultraviolet absorber (C).
  • the adhesive composition of the present invention may be a two-component curable type in which the main component containing the polyurethane resin (A) and the curing agent (B) are separated.
  • the curing agent (B) is a blocked isocyanate
  • the polyurethane resin ( A one-component curable type containing both A) and the curing agent (B) may be used.
  • the adhesive composition of the present invention is a two-component curable type, the ultraviolet absorber (C), the light stabilizer (D), and other components may be contained in the main agent including the polyurethane resin (A). You may mix with a hardening
  • the ratio of the polyurethane resin (A) and the curing agent (B) in the adhesive composition of the present invention is the equivalent ratio NCO / OH between the hydroxyl group of the polyurethane resin (A) and the isocyanate group of the curing agent (B). It is preferably 0 to 5.0, and more preferably 1.5 to 4.0. If the NCO / OH is not less than the lower limit value, the curing reaction of the adhesive composition is likely to proceed. If the NCO / OH is less than or equal to the upper limit, poor curing is unlikely to occur and curing can be performed in a short time.
  • the content of the ultraviolet absorber (C) in the adhesive composition varies depending on the thickness of the adhesive layer to be formed, but is 4 to 11 with respect to 100 parts by mass of the solid content of the polyurethane resin (A) of the present invention. Mass parts are preferred, and 5 to 9 parts by mass are more preferred. If content of a ultraviolet absorber (C) is more than a lower limit, a weather resistance will improve. If content of a ultraviolet absorber (C) is below an upper limit, it will be easy to suppress that adhesive force falls.
  • the content of the light stabilizer (D) in the adhesive composition is preferably 0.2 to 5 parts by mass, and preferably 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin (A). Part is more preferred. If content of a photostabilizer (D) is more than a lower limit, it will become easy to suppress heat degradation and light degradation of a ultraviolet absorber. When the content of the light stabilizer (D) is not more than the upper limit, it is possible to suppress the adhesive layer from becoming opaque due to the low solubility of the light stabilizer at a low temperature of about ⁇ 30 ° C.
  • the total concentration of the solid content (non-volatile content) of the adhesive composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 35% by mass in a state in which all components are included, that is, in use. .
  • the state including all components means that when the adhesive composition of the present invention is a two-component curable type, the main agent and the curing agent are mixed when used, and the viscosity is adjusted optimally for gravure coating, etc. Therefore, it means a state in which a solvent is added.
  • the adhesive composition of the present invention is a two-component curable type
  • a main agent having a solid content concentration of 20 to 80% by mass and a curing agent having a solid content concentration of 40 to 100% by mass It is preferable to mix B) and dilute with a diluting solvent as necessary.
  • the adhesive composition of the present invention is the same as an adhesive for so-called dry laminating, which is applied to a film in the same manner as ordinary inks and adhesives, and is laminated after drying at 70 to 120 ° C. for 10 to 120 seconds.
  • a laminate can be produced by the method.
  • the viscosity of the Zahn cup No. 3 is preferably 10 seconds to 35 seconds, more preferably 15 seconds to 30 seconds, at a temperature of 25 ° C., similarly to general inks and adhesives. Therefore, the solid content concentration is adjusted with a solvent as such.
  • a polyester base agent having a hydroxyl group at the terminal a polyester polyurethane base agent, or a polyether polyurethane base agent, and a polyisocyanate curing agent
  • Two-component curable adhesives to be blended are known.
  • the adhesive may not be sufficient for long-term durability typified by moisture and heat resistance, weather resistance during long-term exposure, etc. required for electrical / electronic materials, automotive parts, artificial leather, building materials, etc. Yes, long-term exposure reduces adhesive strength.
  • the adhesive layer formed by the adhesive composition of the present invention contains a polyurethane resin (A) made from polycarbonate polyol (a1) as a main ingredient, and a specific ultraviolet absorbent (C ) And the light stabilizer (D), an excellent ultraviolet absorbing function can be maintained over a long period of time, and the adhesion is hardly lowered even in a wet environment.
  • A polyurethane resin
  • C specific ultraviolet absorbent
  • D light stabilizer
  • the adhesive composition of the present invention is suitable for use in preventing deterioration of an adherend due to ultraviolet light, and particularly suitable for use outdoors. Specifically, it can be suitably used for applications such as protective films for various printed materials and display materials, and surface materials and back materials of solar cell modules. It is particularly useful for laminating a fluororesin film that transmits light in the ultraviolet region.
  • FIG. 1 is a cross-sectional view showing a laminated body 10 which is an example of the laminated body of the present invention.
  • the laminate 10 includes a first base material 11, an adhesive layer 12, and a second base material 13 that are stacked in this order.
  • the laminate 10 is used with the first substrate 11 facing outside.
  • the first base material 11 is a base material made of a fluororesin film.
  • the fluororesin constituting the first base material 11 include an ethylene-tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”) and a hexafluoropropylene-tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”).
  • FEP perfluoro (alkyl vinyl ether) -tetrafluoroethylene copolymer
  • PFA perfluoro (alkyl vinyl ether) -tetrafluoroethylene copolymer
  • THV tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer
  • THV tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer
  • THV tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer
  • THV tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer
  • ETFE is especially preferable.
  • the 1st base material 11 may contain a well-known additive etc. suitably in the range which does not prevent the effect of this invention.
  • the thickness of the first base material 11 can be appropriately set according to the use, and is preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more in terms of handleability.
  • the upper limit value of the thickness of the first substrate 11 is preferably 1 mm.
  • 12 micrometers or more are preferable and, as for the thickness of the 1st base material 11, 20 micrometers or more are more preferable.
  • the surface of the first base material 11 on which the adhesive layer 12 is laminated is subjected to surface treatment in advance so that the surface wetting index is 35 mN / m or more, preferably 40 mN / m or more.
  • the surface treatment method include corona discharge treatment (in air, nitrogen, carbon dioxide gas, etc.), plasma treatment (high pressure, low pressure), alkali metal solution treatment, high-frequency sputter etching treatment, and the like.
  • the surface wetness index in this invention means the value measured by the method based on JISK6768 using a wetness index reagent.
  • Examples of the second substrate 13 include a biaxially oriented polypropylene film; an ethylene-vinyl acetate copolymer (EVA) film; a polyethylene naphthalate (PEN) film; a polyethylene terephthalate (PET) film; a nylon film; Biaxially stretched polypropylene film subjected to silica deposition; a film obtained by laminating base films selected from EVA, PET, nylon and PEN; selected from the base film, polyethylene, polypropylene, polyethylene subjected to aluminum deposition, and polypropylene And a laminated film obtained by laminating a sealant film.
  • the base film may be printed.
  • an aluminum vapor deposition film, an alumina vapor deposition film, a silica vapor deposition film, an aluminum foil, etc. may be sufficient.
  • the same fluororesin film as the 1st base material 11 may be sufficient.
  • the second base material 13 is pre-treated with a surface on which the adhesive layer 12 is laminated, and the surface wetness index of the surface is 35 mN / m or more, preferably 40 mN / m. The above is preferable.
  • the thickness of the 2nd base material 13 can be set suitably.
  • the adhesive layer 12 is a layer formed by the above-described adhesive composition of the present invention.
  • the first substrate 11 and the second substrate 13 are bonded via the adhesive layer 12.
  • the thickness of the adhesive layer 12 is preferably 3 to 20 ⁇ m, and more preferably 5 to 10 ⁇ m.
  • coating an adhesive composition on the 1st base material 11 the process of drying the apply
  • a laminating method including a step of bonding the surface to which the composition is applied and the second base material 13 and curing the adhesive composition to form the adhesive layer 12 is exemplified.
  • the method for applying the adhesive composition is not particularly limited, and examples thereof include gravure roll coating.
  • Examples of the method of drying the adhesive composition include a method of drying with a dryer.
  • the drying temperature is preferably 70 to 120 ° C.
  • any conventionally known method can be adopted.
  • a method using a laminate roll can be mentioned.
  • the adhesive layer of the laminate of the present invention is excellent in weather resistance, the excellent ultraviolet absorption function is maintained for a long period of time, and the adhesive force is hardly lowered even in a wet environment. Therefore, it is suitable for the use which prevents deterioration by the ultraviolet-ray of the layer inside an adhesive bond layer, and is especially suitable for the use used outdoors. Specifically, it is suitable as a protective film for various printed materials and display objects, and a surface material and a back material of a solar cell module.
  • the laminate of the present invention is not limited to the laminate 10.
  • a laminate in which one or more substrates are further laminated on the second substrate 13 via an adhesive layer may be used.
  • the adhesive layer on the second substrate 13 is also formed by the adhesive composition of the present invention.
  • the adhesive layer on the second substrate 13 is preferably formed of an adhesive composition that does not contain the ultraviolet absorber (C) or the light stabilizer (D).
  • the solar cell module of this invention is a solar cell module which has the laminated body of this invention as at least one of a surface material and a back surface material.
  • the surface material disposed on the light incident side preferably has the laminate of the present invention.
  • both the surface material arranged on the light incident side and the back material arranged on the opposite side to the light incident side have the laminate of the present invention.
  • the solar cell module 1 of the present embodiment has a filler 30 a and a laminate 10 a that is a surface material sequentially stacked on the light incident side of the solar battery cell 20.
  • a filler 30b and a laminated body 10b as a back material are sequentially laminated.
  • the 1st base material 11a, the adhesive bond layer 12a, and the 2nd base material 13a are laminated
  • the aspect of each part of the laminated body 10a is the same aspect as the laminated body 10, and the preferable aspect is also the same.
  • the laminated body 10a is a surface material of the solar cell module 1, and is provided with the first base material 11a facing outside.
  • a first base material 11b, an adhesive layer 12b, and a second base material 13b are laminated in this order.
  • the aspect of each part of the laminated body 10b is the same aspect as the laminated body 10, and the preferable aspect is also the same.
  • the laminated body 10b is a back surface material of the solar cell module 1, and is provided with the first base material 11b facing outside.
  • a known solar cell can be used.
  • an amorphous silicon (a-Si) thin film photoelectric conversion layer having a high collection efficiency with respect to light on a short wavelength side is used as a top cell, and a long wavelength side is used.
  • Examples include a cell in which an amorphous silicon-germanium (a-SiGe) thin film photoelectric conversion layer having a high collection efficiency with respect to the light is used as a bottom cell, and a laminate of a top cell and a bottom cell is disposed between a pair of conductive layers.
  • Other solar cells include those having a photoelectric conversion layer of copper-indium-gallium-selenium (CIGS) or copper-indium-selenium (CIS) alloy, cadmium-tellurium type (CdTe), cadmium. -Sulfur type (CdS), pn junction type or pin junction type semiconductors of the so-called organic solar cell type.
  • CIGS copper-indium-gallium-selenium
  • CIS copper-indium-selenium
  • CdTe copper-indium-selenium
  • CdTe copper-indium-selenium
  • CdS cadmium-tellurium type
  • CdS cadmium.
  • pn junction type or pin junction type semiconductors of the so-called organic solar cell type As the fillers 30a and 30b, known fillers can be used, and examples thereof include an ethylene-vinyl acetate copolymer (EVA) sheet.
  • EVA ethylene-viny
  • the solar cell module 1 can be manufactured by a known manufacturing method such as a laminate method, except that the laminated body 10a and the laminated body 10b are used as the front surface material and the back surface material.
  • the solar cell module of the present invention described above uses the laminate of the present invention having an adhesive layer that can maintain a high adhesion and an excellent ultraviolet absorbing function over a long period of time as at least one of the front surface material and the back surface material. Therefore, it has excellent weather resistance.
  • Examples 1 to 18 are examples, and examples 19 to 39 are comparative examples.
  • [Use ingredients] The components used in the examples and comparative examples are shown below.
  • Polycarbonate polyol (a1) a polycarbonate diol using 3-methyl-1,5-pentanediol as a raw material, 1,6-pentanediol as a chain extender (a2), and isophorone diisocyanate as an organic diisocyanate (a3) It is a polyurethane resin obtained by reacting (IPDI). Further, ⁇ -glycidoxypropyltriethoxysilane is contained as an adhesion promoter.
  • A-1102 Trade name “Takelac A-1102” (solid content 50% by mass, manufactured by Mitsui Chemicals).
  • the solvent is ethyl acetate, and the main component is a nurate of IPDI and hexamethylene diisocyanate (HDI).
  • A-3070 Trade name “Takenate A-3070” (isocyanate content: 15 mass%, solid content 75 mass%, manufactured by Mitsui Chemicals, Inc.).
  • the solvent is ethyl acetate, and the main component is HDI nurate.
  • NT-258 Product name “Crisbon NT258” (solid content 50 mass%, manufactured by DIC Corporation).
  • AD-76P1 Product name “AD-76P1” (manufactured by Toyo Morton). It is a polyester resin having a solid content of 55% by mass, in which the terminal of a polyester resin composed of suberic acid, isophthalic acid, terephthalic acid and ethylene glycol is epoxy-modified with bisphenol A.
  • A-515 Takelac A-515 (polyester polyol, solid content 60 mass%, manufactured by Mitsui Chemicals).
  • (Curing agent (Y)) 2096 Product name “Coronate 2096” (manufactured by Nippon Polyurethane Co., Ltd.). It is an aliphatic hexamethylene diisocyanate having a solid content of 90% by mass.
  • CAT10 Product name “CAT10” (manufactured by Toyo Morton). It is an aromatic tolylene diisocyanate having a solid content of 75% by mass.
  • A-50 Product name “Takenate A-50” (xylene diisocyanate, solid content 75% by mass, manufactured by Mitsui Chemicals, Inc.).
  • TINUVIN 479 Product name “TINUVIN 479” (hydroxyphenyltriazine ultraviolet absorber, manufactured by Ciba Japan).
  • TINUVIN 477 Product name “TINUVIN 477” (hydroxyphenyltriazine-based ultraviolet absorber, manufactured by Ciba Japan).
  • TINUVIN PS Product name “TINUVIN PS” (benzotriazole ultraviolet absorber, manufactured by Ciba Japan).
  • HALS 123 Light stabilizer (D) HALS 123: Product name “TINUVIN 123” (hindered amine light stabilizer, manufactured by Ciba Japan).
  • Example 1 100 parts by mass (solid content) of HD-1013 as the main polyurethane resin (A), 18.8 parts by mass (solid content) of H-62 as the curing agent (B), and UV absorber (C) 7 parts by mass of TINUVIN 479 and 1.5 parts by mass of HALS 123 as the light stabilizer (D) were mixed to prepare an adhesive composition.
  • a 25 ⁇ m-thick ETFE film (trade name: Aflex, manufactured by Asahi Glass Co., Ltd.) subjected to corona discharge treatment, the adhesive composition is dried to a coating thickness of 5 ⁇ m with an applicator. Coated so that.
  • the ETFE film (trade name: Aflex, manufactured by Asahi Glass Co., Ltd.) having a thickness of 25 ⁇ m, which was dried with a dryer at 70 ° C. for 2 minutes and subjected to the same corona discharge treatment as described above, was brought to a nip temperature of 70 ° C.
  • the laminated laminate was pressed and held at 40 ° C. for 48 hours to obtain a laminate.
  • the ETFE film of the counterpart material had a corona discharge treated surface in contact with the adhesive composition.
  • the corona discharge treatment surface of each ETFE film had a surface wetting index of 40 mN / m.
  • the surface wetting index was measured according to JIS K6768 using a wetting index reagent manufactured by Wako Pure Chemical Industries.
  • the obtained laminate was used for evaluation of weather resistance described later.
  • Examples 2 to 39 The laminate was prepared in the same manner as in Example 1 except that the composition and coating thickness of the adhesive composition and the type of the counterpart material laminated on the ETFE film coated with the adhesive composition were changed as shown in Tables 1 to 3. It produced and used for the weather resistance evaluation mentioned later.
  • Teijin Polyester Film TYPE G2C corona-treated product, manufactured by Teijin Limited
  • Teijin Limited which is a PET film having a thickness of 25 ⁇ m
  • the light source is a sunshine carbon arc lamp, operated with an irradiance of 255 W / m 2 (300-700 nm), BPT (black panel temperature) of 63 ° C., and from 48 minutes of light irradiation, 12 minutes of light irradiation and rainfall The total 60 minute cycle was repeated for 1000 hours.
  • an exposure mode an exposure mode in which light and water hit the ETFE film surface was adopted.
  • UV transmittance The laminate of each example was measured for ultraviolet transmittance (unit:%) at a wavelength of 360 nm using a UV-3600 measuring instrument manufactured by Shimadzu Corporation.
  • the ultraviolet transmittance at a wavelength of 360 nm of the ETFE film alone having a thickness of 25 ⁇ m before the laminate was 93%, and the ultraviolet transmittance at a wavelength of 360 nm of the PET film alone having a thickness of 25 ⁇ m was 88%. It shows that the ultraviolet-ray absorption performance of an adhesive bond layer is so high that the ultraviolet-ray transmittance of a laminated body is low. If the transmittance of ultraviolet rays having a wavelength of 360 nm or less can be suppressed to within 20%, more preferably within 10%, the light deterioration of most plastics can be suppressed.
  • Adhesion The adhesion of the laminates of each example was evaluated by measuring peel strength (180 degree peel, peel rate 50 cm / min) (unit: N / cm).
  • the adhesion When the adhesion is 3 N / cm or more and ⁇ Y ⁇ I is 1 or less, it can be evaluated that the adhesion is maintained and the laminate has little discoloration. In particular, it is an essential evaluation item for the back sheet of a solar cell. Moreover, not only the color change of a laminated body but the ultraviolet-ray transmittance of wavelength 360nm was also made into evaluation object. In this test, it is considered that the ultraviolet transmittance changes due to the wet heat deterioration of the adhesive layer and the PET film and the volatilization by the heat of the ultraviolet absorber. The evaluation results of each example are shown in Tables 1 to 3.
  • the compounding amount of each component of the adhesive composition shown in Tables 1 to 3 is the mass (unit: part by mass) of the solid content. Moreover, what was evaluated as “destructed” after the accelerated weather resistance test indicates that the PET film was cracked and was broken.
  • Examples 1 to 18 which are the adhesive compositions of the present invention have accelerated weather resistance compared to Examples 19 to 39 which are adhesive compositions other than the adhesive composition of the present invention.
  • the adhesion and color difference after 1000 hours were both good, and the high ultraviolet absorption ability was maintained. Similar results were obtained in Examples 1 to 3 using an ETFE film as a counterpart material and Examples 6 to 9 using a PET film as a counterpart material.
  • the laminate in which the adhesive layer formed by the adhesive composition of the present invention is laminated on a substrate made of a resin film such as a fluororesin film maintains a high adhesion and an excellent ultraviolet absorbing function over a long period of time. It is possible to prevent the adherend from being deteriorated by ultraviolet rays, and can be used for protective films for various printed materials and display materials, surface materials for solar cell modules, and the like. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-046184 filed on March 3, 2011 is cited here as the disclosure of the specification of the present invention. Incorporated.

Abstract

Provided are an adhesive composition capable of forming an adhesive layer that can maintain a high adhesion force and an excellent ultraviolet absorbing function over a long period of time, a laminated body having an adhesive layer formed of the adhesive composition, and a solar battery module having the laminated body. The adhesive composition includes a polyurethane resin made from a polycarbonate polyol, a curing agent, a triazine series ultraviolet absorbing agent, and a light stabilizer. A laminated body (10) is formed by laminating a first base material (11), an adhesive layer (12) formed of the adhesive composition, and a second base material (13) in this order. The solar battery module has the laminated body (10) as at least one of front and rear surface materials.

Description

接着剤組成物、積層体および太陽電池モジュールAdhesive composition, laminate and solar cell module
　本発明は、接着剤組成物、積層体および太陽電池モジュールに関する。 The present invention relates to an adhesive composition, a laminate, and a solar cell module.
　フッ素樹脂フィルムは優れた耐候性を有しており、例えば１０年の屋外暴露においても透明性や機械強度を良好に保持できる。そのため、例えば、各種印刷物や表示物の表面に積層される保護フィルムとして用いられる。また、近年ではガラスに代わって太陽電池モジュールの表面材に使用されてきている。フッ素樹脂フィルムを使用する表面材は、太陽電池セルを保護するエチレン－酢酸ビニル共重合体（ＥＶＡ）シートや接着性を高めたポリエチレンシートに、接着剤を使用せずに、１４０℃～１６０℃程度の温度で直接フッ素樹脂フィルムを熱圧着するラミネート方式で製造される。しかし、この表面材は、フッ素樹脂フィルムの水蒸気の遮断性（水蒸気バリア性）が不充分なため、ガラスを用いた表面材と比較して水蒸気の遮断性が劣っている。 Fluoropolymer film has excellent weather resistance, and can maintain good transparency and mechanical strength even after outdoor exposure for 10 years, for example. Therefore, for example, it is used as a protective film laminated on the surface of various printed materials and display materials. In recent years, it has been used as a surface material for solar cell modules in place of glass. The surface material that uses a fluororesin film is an ethylene-vinyl acetate copolymer (EVA) sheet that protects solar cells and a polyethylene sheet that has improved adhesiveness, without using an adhesive. It is manufactured by a laminating method in which a fluororesin film is directly thermocompression bonded at a certain temperature. However, this surface material is inferior in water vapor barrier property compared to a surface material using glass because the water vapor barrier property (water vapor barrier property) of the fluororesin film is insufficient.
　そこで、表面材のフッ素樹脂フィルムに、水蒸気バリアフィルムとしてポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンナフタレート（ＰＥＮ）フィルム、ポリエチレン（ＰＥ）フィルム等を積層することが提案されている。しかし、水蒸気バリア性を有するＰＥＴフィルム等のフィルムの耐候性は２年程度であり、耐候性を高めるためには紫外線をカットする必要がある。そこで、ＰＥＴフィルムをフッ素樹脂フィルムと積層する際の接着剤組成物に紫外線吸収性を持たせること、例えば紫外線吸収剤とＥＶＡを含有する接着剤組成物を使用することが提案されている（特許文献１、２参照）。
　また、太陽電池用の裏面材として、透明なフッ素樹脂フィルムの少なくとも一方の面上に、少なくとも無機酸化物層、接着層、電気絶縁層が順次積層され、耐候性を向上させる目的で、前記接着層に該接着層を構成する樹脂固形分１００質量部に対して有機紫外線吸収剤が０．１質量部以上１０質量部以下含有された裏面材が提案されている（特許文献３参照）。この裏面材の接着層には、ポリウレタン系接着剤とトリアゾール系の有機紫外線吸収剤を含有する接着剤組成物が用いられている。
　これらの接着剤組成物には、長期間に亘って安定した接着状態を維持するとともに、高い紫外線吸収機能を持続することが求められる。特に、太陽電池の表面材や裏面材の用途においては、最低でも１０００時間の促進耐候性試験および８５℃で相対湿度８５％の恒温恒湿試験において、変色や密着力の低下を低減できることが重要である。 Accordingly, it has been proposed to laminate a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a polyethylene (PE) film, or the like as a water vapor barrier film on a fluororesin film as a surface material. However, the weather resistance of a film such as a PET film having a water vapor barrier property is about 2 years, and it is necessary to cut ultraviolet rays in order to improve the weather resistance. Therefore, it has been proposed that the adhesive composition when laminating the PET film with the fluororesin film has ultraviolet absorptivity, for example, the use of an adhesive composition containing an ultraviolet absorber and EVA (patent) References 1 and 2).
In addition, as a back material for a solar cell, at least an inorganic oxide layer, an adhesive layer, and an electrical insulating layer are sequentially laminated on at least one surface of a transparent fluororesin film, and the adhesion is performed in order to improve weather resistance. A back material in which an organic ultraviolet absorber is contained in an amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of resin solids constituting the adhesive layer in the layer has been proposed (see Patent Document 3). For the adhesive layer of the back material, an adhesive composition containing a polyurethane adhesive and a triazole organic ultraviolet absorber is used.
These adhesive compositions are required to maintain a stable adhesion state over a long period of time and to maintain a high ultraviolet absorption function. In particular, in the use of solar cell front and back materials, it is important to be able to reduce discoloration and decrease in adhesion in accelerated weathering tests of at least 1000 hours and constant temperature and humidity tests at 85 ° C. and a relative humidity of 85%. It is.
　また、太陽電池用途以外でも、フッ素樹脂フィルム上に、紫外線吸収性の接着剤層を形成した積層体として以下のものが開示されている。
　特許文献４には、４フッ化エチレン共重合樹脂フィルムと塩化ビニル系樹脂フィルムとが、少なくとも紫外線吸収型アクリル系樹脂層を介して積層された建材用基材が開示されている（特許文献４参照）。紫外線吸収型アクリル系樹脂としては、紫外線吸収能を有する反応性ベンゾフェノン系化合物または反応性ベンゾトリアゾール系化合物と、重合性不飽和基を有するアクリル系モノマーとの共重合体が用いられている。
　特許文献５には、エチレン－４フッ化エチレン共重合体を主成分とする樹脂フィルム上に、前記紫外線吸収型アクリル系樹脂と熱接着性樹脂を主成分とする被覆層を設けた表面保護フィルムが開示されている。 Moreover, the following are also disclosed as a laminate in which an ultraviolet-absorbing adhesive layer is formed on a fluororesin film other than for solar cell applications.
Patent Document 4 discloses a building material base material in which a tetrafluoroethylene copolymer resin film and a vinyl chloride resin film are laminated via at least an ultraviolet absorption acrylic resin layer (Patent Document 4). reference). As the ultraviolet absorbing acrylic resin, a copolymer of a reactive benzophenone compound or a reactive benzotriazole compound having an ultraviolet absorbing ability and an acrylic monomer having a polymerizable unsaturated group is used.
Patent Document 5 discloses a surface protective film in which a coating layer mainly composed of the ultraviolet-absorbing acrylic resin and the heat-adhesive resin is provided on a resin film mainly composed of an ethylene-tetrafluoroethylene copolymer. Is disclosed.
日本特許第３９７８９１２号公報Japanese Patent No. 3978912 日本特許第３５３０５９５号公報Japanese Patent No. 3530595 日本特開２００８－２７０６４７号公報Japanese Unexamined Patent Publication No. 2008-270647 日本特開平１０－２０５０５６号公報Japanese Patent Laid-Open No. 10-205056 日本特許第３７１８９０１号公報Japanese Patent No. 3718901
　しかし、特許文献１、２のような接着剤組成物では、ＥＶＡから紫外線吸収剤が経時的に揮発するため、ＰＥＴフィルム等が紫外線によって劣化して着色し、太陽電池の変換効率を低下させてしまう。また、密着性も低下しやすい。
　また、特許文献３～５で用いられる接着剤組成物は、耐候性が不充分であるため、密着力と紫外線吸収機能を長期間維持できない。 However, in the adhesive composition as in Patent Documents 1 and 2, since the ultraviolet absorber volatilizes from EVA over time, the PET film or the like is deteriorated and colored by the ultraviolet ray, and the conversion efficiency of the solar cell is lowered. End up. In addition, the adhesion tends to decrease.
In addition, since the adhesive compositions used in Patent Documents 3 to 5 have insufficient weather resistance, the adhesion and ultraviolet absorption function cannot be maintained for a long time.
　本発明は、太陽電池用途等に使用できる接着剤組成物として、高い密着力と優れた紫外線吸収機能を長期間に亘って持続できる接着剤層を形成できる接着剤組成物の提供を目的とする。
　また、本発明は、フッ素樹脂フィルム等の樹脂フィルムからなる基材に、前記接着剤組成物により形成された接着剤層が積層され、高い密着力と優れた紫外線吸収機能を長期間に亘って持続できる積層体、および該積層体を用いた太陽電池モジュールの提供を目的とする。 An object of the present invention is to provide an adhesive composition that can form an adhesive layer that can maintain a high adhesion and an excellent ultraviolet absorption function over a long period of time as an adhesive composition that can be used for solar cell applications and the like. .
In the present invention, an adhesive layer formed of the adhesive composition is laminated on a substrate made of a resin film such as a fluororesin film, and has high adhesion and excellent ultraviolet absorption function over a long period of time. It aims at providing the laminated body which can be sustained, and the solar cell module using this laminated body.
　本発明は、前記課題を解決するために以下の構成を採用した。
［１］ポリカーボネートポリオール（ａ１）を原料とするポリウレタン樹脂（Ａ）と、硬化剤（Ｂ）と、トリアジン系紫外線吸収剤（Ｃ）と、光安定剤（Ｄ）とを含有する接着剤組成物。［２］前記硬化剤（Ｂ）が、イソシアヌレート体を含む、［１］に記載の接着剤組成物。［３］前記トリアジン系紫外線吸収剤（Ｃ）がヒドロキシフェニルトリアジン系紫外線吸収剤を含む、［１］または［２］に記載の接着剤組成物。［４］前記ヒドロキシフェニルトリアジン系紫外線吸収剤が、２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジンを含む、［３］に記載の接着剤組成物。［５］前記光安定剤（Ｄ）がヒンダードアミン系光安定剤を含む、［１］～［４］のいずれか一項に記載の接着剤組成物。［６］前記ポリウレタン樹脂（Ａ）の水酸基と、前記硬化剤（Ｂ）のイソシアネート基との当量比ＮＣＯ／ＯＨが、１．０～５．０である、［１］～［５］のいずれか一項に記載の接着剤組成物。［７］前記トリアジン系紫外線吸収剤（Ｃ）の含有量が、ポリウレタン樹脂（Ａ）の固形分１００質量部に対して、４～１１質量部である、［１］～［６］のいずれか一項に記載の接着剤組成物。［８］前記光安定剤（Ｄ）の含有量が、ポリウレタン樹脂（Ａ）の固形分１００質量部に対して、０．２～５質量部である、［１］～［７］のいずれか一項に記載の接着剤組成物。［９］フッ素樹脂フィルムからなる基材と、［１］～［８］のいずれか一項に記載の接着剤組成物により前記基材上に形成された接着剤層とを有する積層体。［１０］前記フッ素樹脂フィルムが、エチレン－テトラフルオロエチレン系共重合体フィルムである、［９］に記載の積層体。［１１］前記［９］または［１０］に記載の積層体を表面材および裏面材の少なくとも一方として有する太陽電池モジュール。 The present invention employs the following configuration in order to solve the above problems.
[1] Adhesive composition containing polyurethane resin (A) using polycarbonate polyol (a1) as a raw material, curing agent (B), triazine-based ultraviolet absorber (C), and light stabilizer (D) . [2] The adhesive composition according to [1], wherein the curing agent (B) includes an isocyanurate body. [3] The adhesive composition according to [1] or [2], wherein the triazine-based ultraviolet absorber (C) includes a hydroxyphenyltriazine-based ultraviolet absorber. [4] The hydroxyphenyltriazine ultraviolet absorber is 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5 -The adhesive composition according to [3], comprising triazine. [5] The adhesive composition according to any one of [1] to [4], wherein the light stabilizer (D) includes a hindered amine light stabilizer. [6] Any of [1] to [5], wherein the equivalent ratio NCO / OH between the hydroxyl group of the polyurethane resin (A) and the isocyanate group of the curing agent (B) is 1.0 to 5.0. The adhesive composition according to claim 1. [7] Any of [1] to [6], wherein the content of the triazine-based ultraviolet absorber (C) is 4 to 11 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin (A). The adhesive composition according to one item. [8] Any of [1] to [7], wherein the content of the light stabilizer (D) is 0.2 to 5 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin (A). The adhesive composition according to one item. [9] A laminate having a base material made of a fluororesin film and an adhesive layer formed on the base material by the adhesive composition according to any one of [1] to [8]. [10] The laminate according to [9], wherein the fluororesin film is an ethylene-tetrafluoroethylene copolymer film. [11] A solar cell module having the laminate according to [9] or [10] as at least one of a front material and a back material.
　本発明の接着剤組成物は、太陽電池用途等に使用できる接着剤組成物として、高い密着力と優れた紫外線吸収機能を長期間に亘って持続できる接着剤層を形成できる。
　また、本発明の積層体は、フッ素樹脂フィルム等の樹脂フィルムからなる基材に本発明の接着剤組成物により形成された接着剤層が積層されているため、高い密着力と優れた紫外線吸収機能を長期間に亘って持続できる。
　また、本発明の太陽電池モジュールは、本発明の積層体を有しているため、優れた耐候性を長期間に亘って持続できる。 The adhesive composition of the present invention can form an adhesive layer that can maintain a high adhesion and an excellent ultraviolet absorbing function over a long period of time as an adhesive composition that can be used for solar cell applications and the like.
In addition, since the laminate of the present invention has an adhesive layer formed of the adhesive composition of the present invention laminated on a substrate made of a resin film such as a fluororesin film, it has high adhesion and excellent ultraviolet absorption. The function can be maintained for a long time.
Moreover, since the solar cell module of this invention has the laminated body of this invention, it can maintain the outstanding weather resistance over a long period of time.
本発明の積層体の一例を示した断面図である。It is sectional drawing which showed an example of the laminated body of this invention. 本発明の太陽電池モジュールの一例を示した断面図である。It is sectional drawing which showed an example of the solar cell module of this invention.
　本明細書においては、特に説明しない限り、式（１）で表される化合物を化合物（１）と示し、他の式についても同様に示す。 In the present specification, unless otherwise specified, the compound represented by the formula (1) is referred to as a compound (1), and other formulas are also shown in the same manner.
＜接着剤組成物＞
　本発明の接着剤組成物は、ポリカーボネートポリオール（ａ１）を原料とするポリウレタン樹脂（Ａ）と、硬化剤（Ｂ）と、トリアジン系紫外線吸収剤（Ｃ）（以下、単に「紫外線吸収剤（Ｃ）」ということがある。）と、光安定剤（Ｄ）とを含有する。 <Adhesive composition>
The adhesive composition of the present invention comprises a polyurethane resin (A) using a polycarbonate polyol (a1) as a raw material, a curing agent (B), a triazine-based ultraviolet absorber (C) (hereinafter simply referred to as “UV absorber (C ) "And a light stabilizer (D).
［ポリウレタン樹脂（Ａ）］
　ポリウレタン樹脂（Ａ）は、ポリカーボネートポリオール（ａ１）を原料とするポリウレタン樹脂である。
　ポリウレタン樹脂（Ａ）は、ポリカーボネートポリオール（ａ１）とアルキレンジオール鎖伸長剤（ａ２）（以下、「鎖伸長剤（ａ２）」ということがある。）と有機ジイソシアネート（ａ３）を反応させて得られるポリウレタン樹脂（Ａ１）、またはポリカーボネートポリオール（ａ１）と有機ジイソシアネート（ａ３）を反応させて得られるポリウレタン樹脂（Ａ２）が好ましい。 [Polyurethane resin (A)]
The polyurethane resin (A) is a polyurethane resin using the polycarbonate polyol (a1) as a raw material.
The polyurethane resin (A) is obtained by reacting a polycarbonate polyol (a1), an alkylene diol chain extender (a2) (hereinafter sometimes referred to as “chain extender (a2)”) and an organic diisocyanate (a3). Polyurethane resin (A1) or polyurethane resin (A2) obtained by reacting polycarbonate polyol (a1) and organic diisocyanate (a3) is preferred.
　ポリカーボネートポリオール（ａ１）としては、ジオールと短鎖ジアルキルカーボネートとの反応により得られるポリカーボネートポリオールが挙げられる。
　前記短鎖ジアルキルカーボネートとしては、例えば、ジメチルカーボネート、ジエチルカーボネート等の炭素数１～４のアルキル基を有するジアルキルカーボネートが挙げられる。
　ポリカーボネートポリオール（ａ１）の形成に使用する前記短鎖ジアルキルカーボネートは１種のみであっても２種以上であってもよい。また、ポリカーボネートポリオール（ａ１）が有するアルキル基は、直鎖構造であっても分岐構造であってもよい。 Examples of the polycarbonate polyol (a1) include a polycarbonate polyol obtained by a reaction between a diol and a short-chain dialkyl carbonate.
Examples of the short-chain dialkyl carbonate include dialkyl carbonates having an alkyl group having 1 to 4 carbon atoms such as dimethyl carbonate and diethyl carbonate.
The short-chain dialkyl carbonate used for forming the polycarbonate polyol (a1) may be only one kind or two or more kinds. Moreover, the alkyl group which polycarbonate polyol (a1) has may have a linear structure or a branched structure.
　ポリカーボネートポリオール（ａ１）の形成に使用するジオールとしては、接着強度が向上する点から、分岐アルキル側鎖を有するジオールが好ましい。前記分岐アルキル側鎖を有するジオールとしては、例えば、２－メチル－１，３－プロパンジオール、３－メチル－１，５－ペンタンジオール、２，４－ジエチル－１，５－ペンタンジオールおよび２－ブチル－２－エチル－１，３－プロパンジオール等が挙げられる。
　また、前記分岐アルキル側鎖を有するジオール以外にも、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール等の分岐アルキル側鎖を有さないジオールを使用してもよい。
　ポリカーボネートポリオール（ａ１）の形成に使用するジオールは、１種のみであっても２種以上であってもよい。 As the diol used for forming the polycarbonate polyol (a1), a diol having a branched alkyl side chain is preferable from the viewpoint of improving the adhesive strength. Examples of the diol having a branched alkyl side chain include 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2- And butyl-2-ethyl-1,3-propanediol.
In addition to the diol having a branched alkyl side chain, it does not have a branched alkyl side chain such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Diols may be used.
The diol used for forming the polycarbonate polyol (a1) may be only one type or two or more types.
　ポリカーボネートポリオール（ａ１）におけるジオールに由来する単位の総モル数に対する前記分岐アルキル側鎖を有するジオールに由来する単位のモル数は、２０モル％以上が好ましく、３０モル％以上がより好ましい。前記分岐アルキル側鎖を有するジオールに由来する単位のモル数が下限値以上であれば、接着強度が向上する。 The number of moles of units derived from the diol having a branched alkyl side chain relative to the total number of moles of units derived from the diol in the polycarbonate polyol (a1) is preferably 20 mol% or more, and more preferably 30 mol% or more. If the number of moles of the unit derived from the diol having a branched alkyl side chain is not less than the lower limit value, the adhesive strength is improved.
　ポリカーボネートポリオール（ａ１）の重量平均分子量は、４００～８，０００が好ましく、７００～５，０００がより好ましい。前記重量平均分子量が下限値以上であれば、実用的な合成溶剤に対する溶解性がより良好になる。一方、前記重量平均分子量が上限値以下であれば、充分な接着強度が得られやすく実用性が向上する。 The weight average molecular weight of the polycarbonate polyol (a1) is preferably 400 to 8,000, more preferably 700 to 5,000. If the said weight average molecular weight is more than a lower limit, the solubility with respect to a practical synthesis solvent will become more favorable. On the other hand, if the weight average molecular weight is not more than the upper limit value, sufficient adhesive strength can be easily obtained and the practicality is improved.
　ポリカーボネートポリオール（ａ１）の水酸基価は、１４～２８０ｍｇ／ＫＯＨが好ましく、２２～１６０ｍｇ／ＫＯＨがより好ましい。ポリカーボネートポリオール（ａ１）の水酸基価が下限値以上であれば、架橋反応が充分に進みやすく、生成物の分子量分布が狭くなり、架橋後の耐加水分解性がより良好になる。また、ポリカーボネートポリオール（ａ１）の水酸基価が上限値以下であれば、架橋反応において高分子量生成物が生じ難く、フッ素フィルムに追従する柔軟性を有する接着剤層ができやすい。 The hydroxyl value of the polycarbonate polyol (a1) is preferably 14 to 280 mg / KOH, more preferably 22 to 160 mg / KOH. When the hydroxyl value of the polycarbonate polyol (a1) is at least the lower limit value, the crosslinking reaction is sufficiently facilitated, the molecular weight distribution of the product is narrowed, and the hydrolysis resistance after crosslinking becomes better. Further, when the hydroxyl value of the polycarbonate polyol (a1) is not more than the upper limit value, a high molecular weight product is hardly generated in the crosslinking reaction, and an adhesive layer having flexibility to follow the fluorine film is easily formed.
　鎖伸長剤（ａ２）としては、ポリカーボネートポリオール（ａ１）を形成するジオールとして挙げたものと同じジオールが挙げられ、接着強度が向上する点から、分岐アルキル側鎖を有するジオールが好ましい。
　鎖伸長剤（ａ２）の分子量は、６２～４００が好ましい。これらの中で、好ましい例としては、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－１，３－プロパンジオール、３－メチル－１，５－ペンタンジオール、２，４－ジエチル－１，５－ペンタンジオールおよび２－ブチル－２－エチル－１，３－プロパンジオールが挙げられる。 Examples of the chain extender (a2) include the same diols as those exemplified as the diol forming the polycarbonate polyol (a1). From the viewpoint of improving the adhesive strength, a diol having a branched alkyl side chain is preferable.
The molecular weight of the chain extender (a2) is preferably 62 to 400. Among these, preferred examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3- Mention may be made of methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol.
　鎖伸長剤（ａ２）におけるジオールに由来する単位の総モル数に対する前記分岐アルキル側鎖を有するジオールに由来する単位のモル数は、５モル％以上が好ましく、２０モル％以上がより好ましい。前記分枝アルキル側鎖を有するジオールに由来する単位のモル数が下限値以上であれば、接着強度が向上する。 The number of moles of units derived from the diol having a branched alkyl side chain relative to the total number of moles of units derived from the diol in the chain extender (a2) is preferably 5 mol% or more, and more preferably 20 mol% or more. If the number of moles of units derived from the diol having a branched alkyl side chain is not less than the lower limit value, the adhesive strength is improved.
　有機ジイソシアネート（ａ３）としては、例えば、以下のものが挙げられる。
　芳香族ジイソシアネート（ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、トリレンジイソシアネート、および前記芳香族ジイソシアネートと低分子グリコール類とのプレポリマー等）、
　脂肪族ジイソシアネート（１，６－ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、キシリレンジイソシアネート、リジンジイソシアネート、および前記脂肪族ジイソシアネートと、エチレングリコール、プロピレングリコール等の低分子グリコール類とのプレポリマー等）、
　脂環族ジイソシアネート（イソホロンジイソシアネート、水添化４，４’－ジフェニルメタンジイソシアネート、メチルシクロヘキシレンジイソシアネート、イソプロピリデンジシクロヘキシル－４，４’－ジイソシアネート、および前記脂環族ジイソシアネートと低分子グリコール類とのプレポリマー等）、
　およびこれらの２種以上の混合物等。
　有機ジイソシアネート（ａ３）としては、前記したもののなかでも、耐候性に優れる点から、水添化４，４’－ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート等の脂肪族または脂環族ジイソシアネートが好ましい。 Examples of the organic diisocyanate (a3) include the following.
Aromatic diisocyanates (diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, and prepolymers of said aromatic diisocyanate and low molecular glycols, etc.),
Aliphatic diisocyanates (1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, and the above-mentioned aliphatic diisocyanates and low molecular glycols such as ethylene glycol and propylene glycol Prepolymer),
Alicyclic diisocyanates (isophorone diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, methylcyclohexylene diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate, and prepolymers of the alicyclic diisocyanate and low molecular weight glycols etc),
And a mixture of two or more thereof.
As the organic diisocyanate (a3), aliphatic compounds such as hydrogenated 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc. from the viewpoint of excellent weather resistance among the above-mentioned ones. Alicyclic diisocyanates are preferred.
　ポリウレタン樹脂（Ａ）は、末端に水酸基を有することが好ましい。
　ポリウレタン樹脂（Ａ１）においては、ポリカーボネートポリオール（ａ１）および鎖伸長剤（ａ２）の水酸基と、有機ジイソシアネート（ａ３）のイソシアネート基の当量比（ＮＣＯ／ＯＨ）が、０．７～０．９９であることが好ましく、０．８～０．９７であることがより好ましい。前記ＮＣＯ／ＯＨが下限値以上であれば、接着強度および耐熱性が向上する。また、前記ＮＣＯ／ＯＨが上限値以下であれば、末端に充分な量の水酸基を有する主剤が得られやすい。 The polyurethane resin (A) preferably has a hydroxyl group at the terminal.
In the polyurethane resin (A1), the equivalent ratio (NCO / OH) of the hydroxyl group of the polycarbonate polyol (a1) and the chain extender (a2) to the isocyanate group of the organic diisocyanate (a3) is 0.7 to 0.99. It is preferable that it is 0.8 to 0.97. When the NCO / OH is at least the lower limit value, the adhesive strength and heat resistance are improved. Moreover, if the NCO / OH is not more than the upper limit value, it is easy to obtain a main agent having a sufficient amount of hydroxyl groups at the terminals.
　ポリウレタン樹脂（Ａ１）の場合、鎖伸長剤（ａ２）の使用量は、ポリカーボネートポリオール（ａ１）１００質量部に対して、０．５～５０質量部が好ましい。鎖伸長剤（ａ２）の使用量が下限値以上であれば、接着強度が向上する。鎖伸長剤（ａ２）の使用量が上限値以下であれば、後述する合成溶剤に対する溶解性が向上する。 In the case of the polyurethane resin (A1), the amount of the chain extender (a2) used is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate polyol (a1). If the usage-amount of chain extender (a2) is more than a lower limit, adhesive strength will improve. If the usage-amount of a chain extender (a2) is below an upper limit, the solubility with respect to the synthetic solvent mentioned later will improve.
　ポリウレタン樹脂（Ａ２）においては、ポリカーボネートポリオール（ａ１）の水酸基と有機ジイソシアネート（ａ３）のイソシアネート基の当量比ＮＣＯ／ＯＨが、０．７～０．９９であることが好ましい。前記ＮＣＯ／ＯＨが下限値以上であれば、接着強度および耐熱性が向上する。また、前記ＮＣＯ／ＯＨが上限値以下であれば、末端に充分な量の水酸基を有する主剤が得られやすい。 In the polyurethane resin (A2), the equivalent ratio NCO / OH between the hydroxyl group of the polycarbonate polyol (a1) and the isocyanate group of the organic diisocyanate (a3) is preferably 0.7 to 0.99. When the NCO / OH is at least the lower limit value, the adhesive strength and heat resistance are improved. Moreover, if the NCO / OH is not more than the upper limit value, it is easy to obtain a main agent having a sufficient amount of hydroxyl groups at the terminals.
　ポリウレタン樹脂（Ａ）の水酸基価は、３～２０ｍｇ／ＫＯＨが好ましく、５～１０ｍｇ／ＫＯＨがより好ましい。ポリウレタン樹脂（Ａ）の水酸基価が下限値以上であれば、二液硬化剤として用いられるイソシアネートとの架橋反応が期待できる。ポリウレタン樹脂（Ａ）の水酸基価が上限値以下であれば、二液硬化剤として用いられるイソシアネートとの架橋反応が比較的短時間に、しかも均一に起こりやすい。 The hydroxyl value of the polyurethane resin (A) is preferably 3 to 20 mg / KOH, more preferably 5 to 10 mg / KOH. If the hydroxyl value of the polyurethane resin (A) is at least the lower limit, a crosslinking reaction with an isocyanate used as a two-component curing agent can be expected. When the hydroxyl value of the polyurethane resin (A) is not more than the upper limit value, the crosslinking reaction with the isocyanate used as the two-component curing agent is likely to occur uniformly in a relatively short time.
　ポリウレタン樹脂（Ａ）の重量平均分子量は、４，０００～５０，０００が好ましく、８，０００～１５，０００がより好ましい。ポリウレタン樹脂（Ａ）の重量平均分子量が下限値以上であれば、接着強度が向上する。ポリウレタン樹脂（Ａ）の重量平均分子量が上限値以下であれば、後述する合成溶剤に対する溶解性が向上し、加工性がより良好になる。 The weight average molecular weight of the polyurethane resin (A) is preferably 4,000 to 50,000, and more preferably 8,000 to 15,000. If the weight average molecular weight of a polyurethane resin (A) is more than a lower limit, adhesive strength will improve. If the weight average molecular weight of a polyurethane resin (A) is below an upper limit, the solubility with respect to the synthetic solvent mentioned later will improve, and workability will become more favorable.
　ポリカーボネートポリオール（ａ１）と鎖伸長剤（ａ２）と有機ジイソシアネート（ａ３）の反応は、無溶剤で行ってもよく、イソシアネート基と反応しない合成溶剤中で行ってもよい。また、必要に応じて触媒の存在下で反応を行ってもよい。反応温度は、６０～１５０℃が好ましい。反応時間は、２～１５時間が好ましい。 The reaction of the polycarbonate polyol (a1), the chain extender (a2), and the organic diisocyanate (a3) may be performed without a solvent or in a synthetic solvent that does not react with an isocyanate group. Moreover, you may react in presence of a catalyst as needed. The reaction temperature is preferably 60 to 150 ° C. The reaction time is preferably 2 to 15 hours.
　前記イソシアネート基と反応しない合成溶剤としては、例えば、酢酸エチル、酢酸ブチル、セロソルブアセテート等のエステル類；アセトン、メチルエチルケトン、イソブチルケトン、シクロヘキサノン等のケトン類；テトラヒドロフラン、ジオキサン等のエーテル類；トルエン、キシレン等の芳香族炭化水素類；メチレンクロリド、エチレンクロリド等のハロゲン化炭化水素類；ジメチルスルホキシド、ジメチルスルホアミド等が挙げられる。これらの合成溶剤は、主剤合成後の希釈溶剤としても使用できる。
　ポリウレタン樹脂（Ａ）は、１種を単独で使用してもよく、２種以上を併用してもよい。 Examples of the synthetic solvent that does not react with the isocyanate group include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; toluene and xylene Aromatic hydrocarbons such as methylene chloride, ethylene chloride, and the like; dimethyl sulfoxide, dimethyl sulfoamide, and the like. These synthetic solvents can also be used as a dilution solvent after synthesis of the main agent.
A polyurethane resin (A) may be used individually by 1 type, and may use 2 or more types together.
［硬化剤（Ｂ）］
　硬化剤（Ｂ）としては、例えば、ポリイソシアネートが挙げられる。前記ポリイソシアネートとしては、例えば、有機ジイソシアネート（ａ３）で挙げたジイソシアネートとポリオールとのアダクト体、有機ジイソシアネート（ａ３）で挙げたジイソシアネートのイソシアヌレート体、ビューレット体、アロファネート体等、１分子内にイソシアネート基を２個以上有するものが挙げられる。
　具体的には、例えば、１モルのトリメチロールプロパンに３モルのジイソシアネートを付加して得られるアダクト体、３モルのジイソシアネートに１モルの水を反応させて得られるビューレット体、または３モルのジイソシアネートの重合で得られるイソシアヌレート体等の多官能の有機ポリイソシアネート等が挙げられる。
　硬化剤（Ｂ）としては、イソシアヌレート環構造を含み、イソシアネート基の含有量が１０質量％～２８質量％のイソシアヌレート体が好ましい。
　硬化剤（Ｂ）としては、イソホロンジイソシアネート（ＩＰＤＩ）および／またはヘキサメチレンジイソシアネート（ＨＤＩ）のヌレート体が特に好ましい。 [Curing agent (B)]
Examples of the curing agent (B) include polyisocyanate. Examples of the polyisocyanate include an adduct of a diisocyanate and a polyol exemplified in the organic diisocyanate (a3), an isocyanurate of a diisocyanate exemplified in the organic diisocyanate (a3), a burette, and an allophanate in one molecule. Those having two or more isocyanate groups are exemplified.
Specifically, for example, an adduct obtained by adding 3 mol of diisocyanate to 1 mol of trimethylolpropane, a burette obtained by reacting 1 mol of water with 3 mol of diisocyanate, or 3 mol of Examples thereof include polyfunctional organic polyisocyanates such as isocyanurate obtained by polymerization of diisocyanate.
As the curing agent (B), an isocyanurate body containing an isocyanurate ring structure and having an isocyanate group content of 10% by mass to 28% by mass is preferable.
As the curing agent (B), a nurate body of isophorone diisocyanate (IPDI) and / or hexamethylene diisocyanate (HDI) is particularly preferable.
　硬化剤（Ｂ）は、イソシアネート基がブロック化されたブロック化イソシアネートであってもよい。イソシアネート基のブロック化は、イプシロンカプロラクタム（Ｅ－ＣＡＰ）、メチルエチルケトンオキシム（ＭＥＫ－ＯＸ）、メチルイソブチルケトンオキシム（ＭＩＢＫ－ＯＸ）、ピラリジン、トリアジン（ＴＡ）等によって行える。
　硬化剤（Ｂ）は、１種を単独で使用してもよく、２種以上を併用してもよい。 The curing agent (B) may be a blocked isocyanate in which an isocyanate group is blocked. The isocyanate group can be blocked with epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OX), methyl isobutyl ketone oxime (MIBK-OX), pyraridine, triazine (TA) and the like.
A hardening | curing agent (B) may be used individually by 1 type, and may use 2 or more types together.
［紫外線吸収剤（Ｃ）］
　紫外線吸収剤（Ｃ）は、トリアジン系の紫外線吸収剤である。紫外線吸収剤（Ｃ）としては、紫外線吸収剤として公知のトリアジン誘導体を用いることができ、市販品から入手可能である。紫外線吸収剤（Ｃ）としては、ヒドロキシフェニルトリアジン系紫外線吸収剤が好ましい。ヒドロキシフェニルトリアジン系紫外線吸収剤としては、例えば、下記の紫外線吸収剤が挙げられる。 [Ultraviolet absorber (C)]
The ultraviolet absorber (C) is a triazine-based ultraviolet absorber. As a ultraviolet absorber (C), a well-known triazine derivative can be used as a ultraviolet absorber, and it can obtain from a commercial item. As the ultraviolet absorber (C), a hydroxyphenyltriazine-based ultraviolet absorber is preferable. As a hydroxyphenyl triazine type ultraviolet absorber, the following ultraviolet absorber is mentioned, for example.
　２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジン（市販品としてはチバ・ジャパン社（２０１０年３月１日よりＢＡＳＦジャパン社、以下同様。）製の商品名「ＴＩＮＵＶＩＮ　４７９」。）、
　４－ビス［２－ヒドロキシ－４－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン（下記化合物（１）。市販品としては、チバ・ジャパン社製の商品名「ＴＩＮＵＶＩＮ　４６０」。）、
　２－［４－［（２－ヒドロキシ－３－（２’－エチル）ヘキシルオキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン（下記化合物（２）。市販品としては、チバ・ジャパン社製の商品名「ＴＩＮＵＶＩＮ　４０５」。）、
　チバ・ジャパン社製の商品名「ＴＩＮＵＢＩＮ　４７７」（チバ・ジャパン社の「塗料用添加剤カタログ」（Ｐｕｂ．Ｎｏ．ＣＪ－００５、２００８年３月発行）の第１０頁に記載されている。ヒドロキシフェニルトリアジン系紫外線吸収剤の約８０質量％と、１－メチキシ－２プロピルアセテートの約２０質量％との混合物）、
　チバ・ジャパン社製の商品名「ＴＩＮＵＶＩＮ　４００」（前記「塗料用添加剤カタログ」の第７頁に記載されている。２－（４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－ヒドロキシフェニルと、炭素数１０～１６、主として炭素数１２～１３のアルキル基を有する［（アルキルオキシ）メチル］オキシランとの反応で得られる下記化合物（３）。）等。 2- (2-Hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (commercially available from Ciba Japan (2010) The product name “TINUVIN 479” manufactured by BASF Japan Co., Ltd.
4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (the following compound (1). As a commercial product, manufactured by Ciba Japan Co., Ltd.) Product name "TINUVIN 460"),
2- [4-[(2-Hydroxy-3- (2′-ethyl) hexyloxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (The following compound (2). As a commercial item, trade name “TINUVIN 405” manufactured by Ciba Japan Co., Ltd.).
It is described on page 10 of the trade name “TINUBIN 477” manufactured by Ciba Japan Co., Ltd. (“Catalyst Additive Catalog” of Ciba Japan Co., Ltd. (Pub. No. CJ-005, issued in March 2008)). A mixture of about 80% by weight of a hydroxyphenyltriazine-based UV absorber and about 20% by weight of 1-methoxy-2-propyl acetate),
Product name “TINUVIN 400” manufactured by Ciba Japan Co., Ltd. (described in page 7 of the above-mentioned “Additives catalog for paints”. 2- (4,6-bis (2,4-dimethylphenyl) -1, The following compounds obtained by reaction of 3,5-triazin-2-yl) -5-hydroxyphenyl with [(alkyloxy) methyl] oxirane having an alkyl group having 10 to 16 carbon atoms, mainly 12 to 13 carbon atoms (3).) Etc.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　また、ヒドロキシフェニルトリアジン系紫外線吸収剤以外の好ましい紫外線吸収剤（Ｃ）としては、以下の化合物が挙げられる。
　２－［４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－（オクチルオキシ）フェノール、（市販品としては、サンケミカル社製の商品名「ＣＹＡＳＯＲＢ　ＵＶ－１１６４」。）、
　２－［２，６－ジ（２，４－キシリル）－１，３，５－トリアジン－２－イル］－５－オフチルオキシフェノール（市販品としては、ケミプロ化成社製の商品名「ＫＥＭＩＳＯＲＢ　１０２」。）等。 Moreover, the following compounds are mentioned as preferable ultraviolet absorber (C) other than a hydroxyphenyl triazine type ultraviolet absorber.
2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol (commercially available from Sun Chemical Co., Ltd.) Name “CYASORB UV-1164”)
2- [2,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-offtyloxyphenol (commercially available from Kemipro Kasei Co., Ltd. 102 ".) Etc.
　紫外線吸収剤（Ｃ）としては、耐熱性に優れ、揮発し難い点から、２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジンが好ましい。
　紫外線吸収剤（Ｃ）は、１種を単独で使用してもよく、２種以上を併用してもよい。 As the ultraviolet absorber (C), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) is excellent in heat resistance and hardly volatilizes. ) -1,3,5-triazine is preferred.
A ultraviolet absorber (C) may be used individually by 1 type, and may use 2 or more types together.
［光安定剤（Ｄ）］
　光安定剤（Ｄ）としては、公知のものを使用でき、市販品から入手可能である。光安定剤（Ｄ）としては、ヒンダードアミン系光安定剤、またはヒンダードフェノール系光安定剤が好ましく、ヒンダードアミン系光安定剤がより好ましい。
　ヒンダードアミン系光安定剤としては、例えば、以下のものが挙げられる。
　ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ブチルマロネート（下記化合物（４）。市販品では、チバ・ジャパン社製の商品名「ＴＩＮＵＶＩＮ　１４４」。）、
　チバ・ジャパン社製の商品名「ＴＩＮＵＶＩＮ　１２３」：前記「塗料用添加剤カタログ」の第１６頁に記載されているもので、デカン二酸ビス（２，２，６，６－テトラメチル－１－（オクチルオキシ）－４－ピペリジニル）エステル（１，１－ジメチルエチルヒドロペルオキシド）と、オクタンとの反応生成物（下記化合物（５））等。 [Light stabilizer (D)]
As a light stabilizer (D), a well-known thing can be used and it can obtain from a commercial item. As the light stabilizer (D), a hindered amine light stabilizer or a hindered phenol light stabilizer is preferable, and a hindered amine light stabilizer is more preferable.
Examples of the hindered amine light stabilizer include the following.
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (compound (4) below) In the commercial product, trade name “TINUVIN 144” manufactured by Ciba Japan Co., Ltd.)
Trade name “TINUVIN 123” manufactured by Ciba Japan Co., Ltd., which is described on page 16 of the above “catalyst additive additive catalog”, bis (2,2,6,6-tetramethyl-1) decanedioate -(Octyloxy) -4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) and a reaction product of octane (the following compound (5)) and the like.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　ヒンダードフェノール系光安定剤としては、例えば、ペンタエリスリトール－テトラキス－［３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］（下記化合物（６）。市販品では、チバ・ジャパン社製の商品名「ＩＲＧＡＮＯＸ　１０１０」。）等が挙げられる。 Examples of the hindered phenol light stabilizer include pentaerythritol-tetrakis- [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] (the following compound (6)). Then, trade name “IRGANOX 1010” manufactured by Ciba Japan Co., Ltd.) and the like can be mentioned.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　接着層に光安定剤を含有させる場合、その含有量は、少なすぎると添加効果が充分に得られない、多すぎると光安定剤自身が黄変や硬化を阻害するため、これらの不都合が生じない範囲で設定することが好ましい。例えば本発明の二液反応型ポリウレタン系接着剤の固形分１００質量部に対して、０．１～４．０質量部であることが好ましく、０．５～２．０質量部であることがより好ましい。 When the light stabilizer is contained in the adhesive layer, if the content is too small, the effect of addition cannot be sufficiently obtained, and if it is too large, the light stabilizer itself inhibits yellowing and curing, so these disadvantages occur. It is preferable to set within a range. For example, the amount is preferably 0.1 to 4.0 parts by weight, and more preferably 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the solid content of the two-component reactive polyurethane adhesive of the present invention. More preferred.
［他の成分］
　本発明の接着剤組成物は、本発明の効果を妨げない範囲であれば、前記ポリウレタン樹脂（Ａ）、硬化剤（Ｂ）、紫外線吸収剤（Ｃ）および光安定剤（Ｄ）に加えて、必要に応じて、前記ポリウレタン樹脂（Ａ）、硬化剤（Ｂ）、紫外線吸収剤（Ｃ）および光安定剤（Ｄ）以外の他の成分を含有してもよい。
　他の成分としては、接着促進剤が挙げられる。接着促進剤としては、例えば、シランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤等のカップリング剤、エポキシ樹脂等が挙げられる。なかでも、シランカップリング剤が好ましい。 [Other ingredients]
The adhesive composition of the present invention is in addition to the polyurethane resin (A), the curing agent (B), the ultraviolet absorber (C) and the light stabilizer (D) as long as the effects of the present invention are not hindered. If necessary, other components other than the polyurethane resin (A), the curing agent (B), the ultraviolet absorber (C) and the light stabilizer (D) may be contained.
Another component includes an adhesion promoter. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, and epoxy resins. Of these, a silane coupling agent is preferable.
　シランカップリング剤としては、例えば、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメチルジメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノシラン類；β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン等のエポキシシラン類；ビニルトリス（β－メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン等のビニルシラン類；ヘキサメチルジシラザン、γ－メルカプトプロピルトリメトキシシラン等が挙げられる。なかでも、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン等のエポキシシラン類が好ましい。 Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ. Aminosilanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Epoxy silanes such as glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, - mercaptopropyltrimethoxysilane, and the like. Of these, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane are preferable.
　また、他の成分としては、ポリウレタン樹脂（Ａ）以外の他の樹脂、紫外線吸収剤（Ｃ）以外の他の紫外線吸収剤、反応触媒、消泡剤、レベリング剤、酸化防止剤等が挙げられる。
　なお、本発明の接着剤組成物が含有する樹脂は、ポリウレタン樹脂（Ａ）のみであることが好ましい。また、本発明の接着剤組成物が含有する紫外線吸収剤は紫外線吸収剤（Ｃ）のみであることが好ましい。 Examples of other components include resins other than the polyurethane resin (A), UV absorbers other than the UV absorber (C), reaction catalysts, antifoaming agents, leveling agents, and antioxidants. .
In addition, it is preferable that resin which the adhesive composition of this invention contains is only a polyurethane resin (A). Moreover, it is preferable that the ultraviolet absorber which the adhesive composition of this invention contains is only a ultraviolet absorber (C).
　本発明の接着剤組成物は、ポリウレタン樹脂（Ａ）を含む主剤と硬化剤（Ｂ）を分けた２液硬化型としてもよく、硬化剤（Ｂ）がブロック化イソシアネートの場合等はポリウレタン樹脂（Ａ）と硬化剤（Ｂ）をともに含む１液硬化型としてもよい。本発明の接着剤組成物を２液硬化型とする場合は、紫外線吸収剤（Ｃ）、光安定剤（Ｄ）およびその他の成分は、ポリウレタン樹脂（Ａ）を含む主剤に含有してもよく、硬化剤（Ｂ）と混合してもよい。 The adhesive composition of the present invention may be a two-component curable type in which the main component containing the polyurethane resin (A) and the curing agent (B) are separated. When the curing agent (B) is a blocked isocyanate, the polyurethane resin ( A one-component curable type containing both A) and the curing agent (B) may be used. When the adhesive composition of the present invention is a two-component curable type, the ultraviolet absorber (C), the light stabilizer (D), and other components may be contained in the main agent including the polyurethane resin (A). You may mix with a hardening | curing agent (B).
　本発明の接着剤組成物におけるポリウレタン樹脂（Ａ）と硬化剤（Ｂ）の割合は、ポリウレタン樹脂（Ａ）の水酸基と硬化剤（Ｂ）のイソシアネート基との当量比ＮＣＯ／ＯＨを、１．０～５．０とすることが好ましく、１．５～４．０とすることがより好ましい。前記ＮＣＯ／ＯＨが下限値以上であれば、接着剤組成物の硬化反応が進行しやすい。前記ＮＣＯ／ＯＨが上限値以下であれば、硬化不良が起き難く、短時間で硬化できる。 The ratio of the polyurethane resin (A) and the curing agent (B) in the adhesive composition of the present invention is the equivalent ratio NCO / OH between the hydroxyl group of the polyurethane resin (A) and the isocyanate group of the curing agent (B). It is preferably 0 to 5.0, and more preferably 1.5 to 4.0. If the NCO / OH is not less than the lower limit value, the curing reaction of the adhesive composition is likely to proceed. If the NCO / OH is less than or equal to the upper limit, poor curing is unlikely to occur and curing can be performed in a short time.
　接着剤組成物中の紫外線吸収剤（Ｃ）の含有量は、形成する接着剤層の厚みによっても異なるが、本発明のポリウレタン樹脂（Ａ）の固形分１００質量部に対して、４～１１質量部が好ましく、５～９質量部がより好ましい。紫外線吸収剤（Ｃ）の含有量が下限値以上であれば、耐候性が向上する。紫外線吸収剤（Ｃ）の含有量が上限値以下であれば、接着力が低下することを抑制しやすい。 The content of the ultraviolet absorber (C) in the adhesive composition varies depending on the thickness of the adhesive layer to be formed, but is 4 to 11 with respect to 100 parts by mass of the solid content of the polyurethane resin (A) of the present invention. Mass parts are preferred, and 5 to 9 parts by mass are more preferred. If content of a ultraviolet absorber (C) is more than a lower limit, a weather resistance will improve. If content of a ultraviolet absorber (C) is below an upper limit, it will be easy to suppress that adhesive force falls.
　接着剤組成物中の光安定剤（Ｄ）の含有量は、ポリウレタン樹脂（Ａ）の固形分１００質量部に対して、０．２～５質量部が好ましく、０．５～２．５質量部がより好ましい。光安定剤（Ｄ）の含有量が下限値以上であれば、紫外線吸収剤の熱劣化および光劣化を抑えることが容易になる。光安定剤（Ｄ）の含有量が上限値以下であれば、－３０℃程度の低温時に、接着剤層がその光安定剤の溶解性の低さから不透明になることを抑制できる。 The content of the light stabilizer (D) in the adhesive composition is preferably 0.2 to 5 parts by mass, and preferably 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin (A). Part is more preferred. If content of a photostabilizer (D) is more than a lower limit, it will become easy to suppress heat degradation and light degradation of a ultraviolet absorber. When the content of the light stabilizer (D) is not more than the upper limit, it is possible to suppress the adhesive layer from becoming opaque due to the low solubility of the light stabilizer at a low temperature of about −30 ° C.
　本発明の接着剤組成物の固形分（不揮発分）の合計濃度は、全ての成分を含んだ状態、すなわち使用時の状態において、５～５０質量％が好ましく、１０～３５質量％がより好ましい。なお、全ての成分を含んだ状態とは、本発明の接着剤組成物を２液硬化型とする場合は使用する際に主剤と硬化剤を混ぜ、更に、グラビア塗工等に最適な粘度調整のために、溶剤を加えた状態を意味する。
　より具体的には、本発明の接着剤組成物を２液硬化型とする場合には、固形分濃度が２０～８０質量％の主剤と、固形分濃度が４０～１００質量％の硬化剤（Ｂ）を混合し、必要に応じて希釈溶剤で希釈して使用することが好ましい。 The total concentration of the solid content (non-volatile content) of the adhesive composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 35% by mass in a state in which all components are included, that is, in use. . In addition, the state including all components means that when the adhesive composition of the present invention is a two-component curable type, the main agent and the curing agent are mixed when used, and the viscosity is adjusted optimally for gravure coating, etc. Therefore, it means a state in which a solvent is added.
More specifically, when the adhesive composition of the present invention is a two-component curable type, a main agent having a solid content concentration of 20 to 80% by mass and a curing agent having a solid content concentration of 40 to 100% by mass ( It is preferable to mix B) and dilute with a diluting solvent as necessary.
　本発明の接着剤組成物は、通常のインキおよび接着剤と同じ方法でフィルムに塗工し、７０℃～１２０℃で１０秒～１２０秒乾燥後にラミネートするという、いわゆるドライラミネート用接着剤と同じ方法で積層体を作製することができる。グラビア塗工する場合、ザーンカップ３番の粘度は、温度２５℃において、一般インキや接着剤と同様に、１０秒～３５秒であることが好ましく、１５秒～３０秒であることがより好ましいため、そのように固形分濃度を溶剤により調整する。 The adhesive composition of the present invention is the same as an adhesive for so-called dry laminating, which is applied to a film in the same manner as ordinary inks and adhesives, and is laminated after drying at 70 to 120 ° C. for 10 to 120 seconds. A laminate can be produced by the method. In the case of gravure coating, the viscosity of the Zahn cup No. 3 is preferably 10 seconds to 35 seconds, more preferably 15 seconds to 30 seconds, at a temperature of 25 ° C., similarly to general inks and adhesives. Therefore, the solid content concentration is adjusted with a solvent as such.
　従来から、各種エラストマーやプラスチック基材に対して高接着強度が得られる接着剤として、末端に水酸基を有するポリエステル系主剤、ポリエステルポリウレタン系主剤、またはポリエーテルポリウレタン系主剤と、ポリイソシアネート硬化剤とを配合する２液硬化型接着剤が知られている。しかし、前記接着剤は、電気・電子材料、自動車用部品、人工皮革、建材用途等で求められる、耐湿熱性、長期暴露時の耐候性等に代表される長期耐久性については不充分な場合があり、長期暴露により接着強度が低下する。
　これに対し、本発明の接着剤組成物により形成した接着剤層は、主剤にポリカーボネートポリオール（ａ１）を原料とするポリウレタン樹脂（Ａ）を含み、かつ紫外線吸収剤として特定の紫外線吸収剤（Ｃ）と光安定剤（Ｄ）を含んでいることで、優れた紫外線吸収機能を長期間に亘って持続できるとともに、湿潤環境においても密着力が低下し難い。 Conventionally, as an adhesive capable of obtaining high adhesive strength with respect to various elastomers and plastic substrates, a polyester base agent having a hydroxyl group at the terminal, a polyester polyurethane base agent, or a polyether polyurethane base agent, and a polyisocyanate curing agent Two-component curable adhesives to be blended are known. However, the adhesive may not be sufficient for long-term durability typified by moisture and heat resistance, weather resistance during long-term exposure, etc. required for electrical / electronic materials, automotive parts, artificial leather, building materials, etc. Yes, long-term exposure reduces adhesive strength.
On the other hand, the adhesive layer formed by the adhesive composition of the present invention contains a polyurethane resin (A) made from polycarbonate polyol (a1) as a main ingredient, and a specific ultraviolet absorbent (C ) And the light stabilizer (D), an excellent ultraviolet absorbing function can be maintained over a long period of time, and the adhesion is hardly lowered even in a wet environment.
　本発明の接着剤組成物は、被着体の紫外線による劣化を防ぐ用途に好適であり、特に屋外で用いられる用途に好適である。具体的には、各種印刷物や表示物の保護フィルム、太陽電池モジュールの表面材および裏面材等の用途に好適に使用できる。特に紫外線領域の光を透過するフッ素樹脂フィルムのラミネートに有用である。 The adhesive composition of the present invention is suitable for use in preventing deterioration of an adherend due to ultraviolet light, and particularly suitable for use outdoors. Specifically, it can be suitably used for applications such as protective films for various printed materials and display materials, and surface materials and back materials of solar cell modules. It is particularly useful for laminating a fluororesin film that transmits light in the ultraviolet region.
＜積層体＞
　本発明の積層体は、フッ素樹脂フィルムからなる基材と、前述した本発明の接着剤組成物により前記基材上に形成された接着剤層とを有する。以下、本発明の積層体の一例を示して詳細に説明する。図１は、本発明の積層体の一例である積層体１０を示した断面図である。
　積層体１０は、図１に示すように、第１の基材１１と接着剤層１２と第２の基材１３がこの順に積層されている。積層体１０は、第１の基材１１を外側にして使用する。 <Laminated body>
The laminated body of this invention has the base material which consists of a fluororesin film, and the adhesive bond layer formed on the said base material with the adhesive composition of this invention mentioned above. Hereinafter, an example of the laminate of the present invention will be described in detail. FIG. 1 is a cross-sectional view showing a laminated body 10 which is an example of the laminated body of the present invention.
As shown in FIG. 1, the laminate 10 includes a first base material 11, an adhesive layer 12, and a second base material 13 that are stacked in this order. The laminate 10 is used with the first substrate 11 facing outside.
［基材］
　第１の基材１１は、フッ素樹脂フィルムからなる基材である。
　第１の基材１１を構成するフッ素樹脂としては、例えば、エチレン－テトラフルオロエチレン系共重合体（以下、「ＥＴＦＥ」という。）、ヘキサフルオロプロピレン－テトラフルオロエチレン系共重合体（以下、「ＦＥＰ」という。）、パーフルオロ（アルキルビニルエーテル）－テトラフルオロエチレン系共重合体（以下、「ＰＦＡ」という。）、テトラフルオロエチレン－ヘキサフルオロプロピレン－フッ化ビニリデン系共重合体（以下、「ＴＨＶ」という。）、ポリフッ化ビニリデン、フッ化ビニリデン－ヘキサフルオロプロピレン系共重合体、ポリフッ化ビニル等が挙げられる。なかでも、ＥＴＦＥ、ＦＥＰ、ＰＦＡおよびＴＨＶからなる群から選ばれる１種以上が好ましく、ＥＴＦＥが特に好ましい。
　第１の基材１１は、本発明の効果を妨げない範囲で、公知の添加剤等を適宜含んでもよい。例えば、紫外線吸収剤を含むフッ素樹脂フィルムであってもよい。 [Base material]
The first base material 11 is a base material made of a fluororesin film.
Examples of the fluororesin constituting the first base material 11 include an ethylene-tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”) and a hexafluoropropylene-tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”). FEP ”), perfluoro (alkyl vinyl ether) -tetrafluoroethylene copolymer (hereinafter referred to as“ PFA ”), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (hereinafter referred to as“ THV ”). And vinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyvinyl fluoride, and the like. Especially, 1 or more types chosen from the group which consists of ETFE, FEP, PFA, and THV are preferable, and ETFE is especially preferable.
The 1st base material 11 may contain a well-known additive etc. suitably in the range which does not prevent the effect of this invention. For example, a fluororesin film containing an ultraviolet absorber may be used.
　第１の基材１１の厚さは、用途に応じて適宜設定でき、取り扱い性の点では、１０μｍ以上が好ましく、２０μｍ以上がより好ましい。第１の基材１１の厚さの上限値は１ｍｍが好ましい。また、第１の基材１１を保護フィルムとして用いる場合、第１の基材１１の厚さは、１２μｍ以上が好ましく、２０μｍ以上がより好ましい。 The thickness of the first base material 11 can be appropriately set according to the use, and is preferably 10 μm or more, and more preferably 20 μm or more in terms of handleability. The upper limit value of the thickness of the first substrate 11 is preferably 1 mm. Moreover, when using the 1st base material 11 as a protective film, 12 micrometers or more are preferable and, as for the thickness of the 1st base material 11, 20 micrometers or more are more preferable.
　第１の基材１１における接着剤層１２が積層される面は、予め表面処理を施して、表面濡れ指数を３５ｍＮ／ｍ以上、好ましくは４０ｍＮ／ｍ以上とすることが好ましい。
　表面処理方法としては、コロナ放電処理（空気中、窒素中、炭酸ガス中等）や、プラズマ処理（高圧、低圧）、アルカリ金属溶液処理、高周波スパッタエッチング処理等が挙げられる。
　なお、本発明における表面濡れ指数は、濡れ指数試薬を用いて、ＪＩＳ　Ｋ６７６８に準拠した方法で測定される値を意味する。 It is preferable that the surface of the first base material 11 on which the adhesive layer 12 is laminated is subjected to surface treatment in advance so that the surface wetting index is 35 mN / m or more, preferably 40 mN / m or more.
Examples of the surface treatment method include corona discharge treatment (in air, nitrogen, carbon dioxide gas, etc.), plasma treatment (high pressure, low pressure), alkali metal solution treatment, high-frequency sputter etching treatment, and the like.
In addition, the surface wetness index in this invention means the value measured by the method based on JISK6768 using a wetness index reagent.
　第２の基材１３としては、例えば、２軸延伸ポリプロピレンフィルム；エチレン－酢酸ビニル共重合体（ＥＶＡ）フィルム；ポリエチレンナフタレート（ＰＥＮ）フィルム；ポリエチレンテレフタレート（ＰＥＴ）フィルム；ナイロンフィルム；アルミナ蒸着またはシリカ蒸着が施された２軸延伸ポリプロピレンフィルム；ＥＶＡ、ＰＥＴ、ナイロンおよびＰＥＮから選ばれるベースフィルム同士をラミネートしたフィルム；前記ベースフィルムと、ポリエチレン、ポリプロピレン、アルミニウム蒸着が施されたポリエチレンおよびポリプロピレンから選ばれるシーラントフィルムをラミネートした積層フィルム；等が挙げられる。前記ベースフィルムには、印刷を施してもよい。
　また、アルミニウム蒸着フィルム、アルミナ蒸着フィルム、シリカ蒸着フィルム、アルミニウム箔等であってもよい。また、第１の基材１１と同様のフッ素樹脂フィルムであってもよい。
　なお、可塑剤を大量に含む軟質塩化ビニルに分類される基材は、密着性が得られ難いため、第２の基材１３に適用しないことが好ましい。 Examples of the second substrate 13 include a biaxially oriented polypropylene film; an ethylene-vinyl acetate copolymer (EVA) film; a polyethylene naphthalate (PEN) film; a polyethylene terephthalate (PET) film; a nylon film; Biaxially stretched polypropylene film subjected to silica deposition; a film obtained by laminating base films selected from EVA, PET, nylon and PEN; selected from the base film, polyethylene, polypropylene, polyethylene subjected to aluminum deposition, and polypropylene And a laminated film obtained by laminating a sealant film. The base film may be printed.
Moreover, an aluminum vapor deposition film, an alumina vapor deposition film, a silica vapor deposition film, an aluminum foil, etc. may be sufficient. Moreover, the same fluororesin film as the 1st base material 11 may be sufficient.
In addition, it is preferable not to apply the base material classified into the soft vinyl chloride containing a large amount of plasticizer to the second base material 13 because it is difficult to obtain adhesion.
　第２の基材１３は、第１の基材１１と同様に、接着剤層１２が積層される面を予め表面処理し、該面の表面濡れ指数を３５ｍＮ／ｍ以上、好ましくは４０ｍＮ／ｍ以上とすることが好ましい。
　第２の基材１３の厚みは、適宜設定できる。 Similar to the first base material 11, the second base material 13 is pre-treated with a surface on which the adhesive layer 12 is laminated, and the surface wetness index of the surface is 35 mN / m or more, preferably 40 mN / m. The above is preferable.
The thickness of the 2nd base material 13 can be set suitably.
［接着剤層］
　接着剤層１２は、前述した本発明の接着剤組成物により形成される層である。接着剤層１２を介して第１の基材１１と第２の基材１３が接着される。
　接着剤層１２の厚みは、３～２０μｍが好ましく、５～１０μｍがより好ましい。 [Adhesive layer]
The adhesive layer 12 is a layer formed by the above-described adhesive composition of the present invention. The first substrate 11 and the second substrate 13 are bonded via the adhesive layer 12.
The thickness of the adhesive layer 12 is preferably 3 to 20 μm, and more preferably 5 to 10 μm.
　積層体１０の製造方法としては、例えば、接着剤組成物を第１の基材１１上に塗布する工程と、塗布した接着剤組成物を乾燥する工程と、第１の基材１１の接着剤組成物が塗布された面と第２の基材１３を貼り合わせ、接着剤組成物を硬化して接着剤層１２を形成する工程とを有するラミネート方法が挙げられる。 As a manufacturing method of the laminated body 10, the process of apply | coating an adhesive composition on the 1st base material 11, the process of drying the apply | coated adhesive composition, and the adhesive agent of the 1st base material 11, for example A laminating method including a step of bonding the surface to which the composition is applied and the second base material 13 and curing the adhesive composition to form the adhesive layer 12 is exemplified.
　接着剤組成物を塗布する方法は特に限定されず、例えば、グラビアロール塗工等が挙げられる。
　接着剤組成物を乾燥する方法としては、例えば、ドライヤーで乾燥する方法が挙げられる。乾燥温度は、７０～１２０℃が好ましい。
　第１の基材１１における接着剤組成物が塗布された面と第２の基材１３とを貼り合わせる方法は、従来公知の任意の方法を採用できる。例えば、ラミネートロールを用いる方法が挙げられる。ラミネートロールの温度は、４０～１２０℃が好ましい。
　接着剤組成物を硬化させた後の養生は、４０℃～７０℃で２～１６８時間行うことが好ましい。 The method for applying the adhesive composition is not particularly limited, and examples thereof include gravure roll coating.
Examples of the method of drying the adhesive composition include a method of drying with a dryer. The drying temperature is preferably 70 to 120 ° C.
As a method of bonding the surface of the first substrate 11 on which the adhesive composition is applied and the second substrate 13, any conventionally known method can be adopted. For example, a method using a laminate roll can be mentioned. The temperature of the laminate roll is preferably 40 to 120 ° C.
Curing after curing the adhesive composition is preferably performed at 40 to 70 ° C. for 2 to 168 hours.
　本発明の積層体の接着剤層は、耐候性に優れているので、優れた紫外線吸収機能が長期間保持されるとともに、湿潤環境においても密着力が低下し難い。そのため、接着剤層よりも内側の層の紫外線による劣化を防ぐ用途に好適であり、特に屋外で用いられる用途に好適である。具体的には、各種印刷物や表示物の保護フィルム、太陽電池モジュールの表面材および裏面材として好適である。 Since the adhesive layer of the laminate of the present invention is excellent in weather resistance, the excellent ultraviolet absorption function is maintained for a long period of time, and the adhesive force is hardly lowered even in a wet environment. Therefore, it is suitable for the use which prevents deterioration by the ultraviolet-ray of the layer inside an adhesive bond layer, and is especially suitable for the use used outdoors. Specifically, it is suitable as a protective film for various printed materials and display objects, and a surface material and a back material of a solar cell module.
　なお、本発明の積層体は、前記積層体１０には限定されない。例えば、第２の基材１３上に、さらに１以上の基材が接着剤層を介して積層された積層体であってもよい。その場合、さらに耐候性を向上させる観点では、第２の基材１３上の接着剤層も本発明の接着剤組成物により形成することが好ましい。ただし、コストダウンの観点では、第２の基材１３上の接着剤層は、紫外線吸収剤（Ｃ）や光安定剤（Ｄ）が含有されていない接着剤組成物で形成することが好ましい。 Note that the laminate of the present invention is not limited to the laminate 10. For example, a laminate in which one or more substrates are further laminated on the second substrate 13 via an adhesive layer may be used. In that case, from the viewpoint of further improving the weather resistance, it is preferable that the adhesive layer on the second substrate 13 is also formed by the adhesive composition of the present invention. However, from the viewpoint of cost reduction, the adhesive layer on the second substrate 13 is preferably formed of an adhesive composition that does not contain the ultraviolet absorber (C) or the light stabilizer (D).
［太陽電池モジュール］
　本発明の太陽電池モジュールは、本発明の積層体を表面材および裏面材の少なくとも一方として有する太陽電池モジュールである。
　本発明の太陽電池モジュールは、光入射側に配置される表面材が本発明の積層体を有することが好ましい。また、光入射側に配置される表面材と、光入射側と反対側に配置される裏面材の両方が本発明の積層体を有することが特に好ましい。 [Solar cell module]
The solar cell module of this invention is a solar cell module which has the laminated body of this invention as at least one of a surface material and a back surface material.
In the solar cell module of the present invention, the surface material disposed on the light incident side preferably has the laminate of the present invention. Moreover, it is particularly preferable that both the surface material arranged on the light incident side and the back material arranged on the opposite side to the light incident side have the laminate of the present invention.
　以下、本発明の太陽電池モジュールの一例を示して詳細に説明する。
　本実施形態の太陽電池モジュール１は、図２に示すように、太陽電池セル２０の光入射側に、充填材３０ａと、表面材である積層体１０ａが順次積層されており、光入射側と反対側に、充填材３０ｂと、裏面材である積層体１０ｂが順次積層されている。 Hereinafter, an example of the solar cell module of the present invention will be shown and described in detail.
As shown in FIG. 2, the solar cell module 1 of the present embodiment has a filler 30 a and a laminate 10 a that is a surface material sequentially stacked on the light incident side of the solar battery cell 20. On the opposite side, a filler 30b and a laminated body 10b as a back material are sequentially laminated.
　積層体１０ａは、第１の基材１１ａ、接着剤層１２ａおよび第２の基材１３ａがこの順に積層されている。積層体１０ａの各部分の態様は、前記積層体１０と同じ態様であり、好ましい態様も同じである。積層体１０ａは、太陽電池モジュール１の表面材であり、第１の基材１１ａを外側にして設けられる。
　積層体１０ｂは、第１の基材１１ｂ、接着剤層１２ｂおよび第２の基材１３ｂがこの順に積層されている。積層体１０ｂの各部分の態様は、前記積層体１０と同じ態様であり、好ましい態様も同じである。積層体１０ｂは、太陽電池モジュール１の裏面材であり、第１の基材１１ｂを外側にして設けられる。 As for the laminated body 10a, the 1st base material 11a, the adhesive bond layer 12a, and the 2nd base material 13a are laminated | stacked in this order. The aspect of each part of the laminated body 10a is the same aspect as the laminated body 10, and the preferable aspect is also the same. The laminated body 10a is a surface material of the solar cell module 1, and is provided with the first base material 11a facing outside.
In the laminate 10b, a first base material 11b, an adhesive layer 12b, and a second base material 13b are laminated in this order. The aspect of each part of the laminated body 10b is the same aspect as the laminated body 10, and the preferable aspect is also the same. The laminated body 10b is a back surface material of the solar cell module 1, and is provided with the first base material 11b facing outside.
　太陽電池セル２０としては、公知の太陽電池セルを使用でき、例えば、短波長側の光に対して収集効率が高いアモルファスシリコン（ａ－Ｓｉ）の薄膜光電変換層をトップセルとし、長波長側の光に対して収集効率が高いアモルファスシリコン－ゲルマニウム（ａ－ＳｉＧｅ）の薄膜光電変換層をボトムセルとし、トップセルとボトムセルの積層体を一対の導電層の間に配置したセル等が挙げられる。また他の太陽電池セルとしては、銅－インジウム－ガリウム－セレン（ＣＩＧＳ）や銅－インジウム－セレン（ＣＩＳ）の合金の光電変換層を有するタイプのものや、カドミウム－テルルタイプ（ＣｄＴｅ）、カドミウム－硫黄タイプ（ＣｄＳ）、ｐ－ｎ接合型またはｐ－ｉ－ｎ接合型半導体のいわゆる有機太陽電池タイプのものなどが挙げられる。
　充填材３０ａ、３０ｂとしては、公知の充填材を使用でき、例えば、エチレン－酢酸ビニル共重合体（ＥＶＡ）シート等が挙げられる。 As the solar cell 20, a known solar cell can be used. For example, an amorphous silicon (a-Si) thin film photoelectric conversion layer having a high collection efficiency with respect to light on a short wavelength side is used as a top cell, and a long wavelength side is used. Examples include a cell in which an amorphous silicon-germanium (a-SiGe) thin film photoelectric conversion layer having a high collection efficiency with respect to the light is used as a bottom cell, and a laminate of a top cell and a bottom cell is disposed between a pair of conductive layers. Other solar cells include those having a photoelectric conversion layer of copper-indium-gallium-selenium (CIGS) or copper-indium-selenium (CIS) alloy, cadmium-tellurium type (CdTe), cadmium. -Sulfur type (CdS), pn junction type or pin junction type semiconductors of the so-called organic solar cell type.
As the fillers 30a and 30b, known fillers can be used, and examples thereof include an ethylene-vinyl acetate copolymer (EVA) sheet.
　太陽電池モジュール１は、表面材および裏面材として積層体１０ａおよび積層体１０ｂを用いる以外は、ラミネート方式等の公知の製造方法で製造できる。 The solar cell module 1 can be manufactured by a known manufacturing method such as a laminate method, except that the laminated body 10a and the laminated body 10b are used as the front surface material and the back surface material.
　以上説明した本発明の太陽電池モジュールは、表面材および裏面材の少なくとも一方として、高い密着力と優れた紫外線吸収機能を長期間に亘って持続できる接着剤層を有する本発明の積層体を用いているため、優れた耐候性を有している。 The solar cell module of the present invention described above uses the laminate of the present invention having an adhesive layer that can maintain a high adhesion and an excellent ultraviolet absorbing function over a long period of time as at least one of the front surface material and the back surface material. Therefore, it has excellent weather resistance.
　以下、実施例によって本発明を詳細に説明するが、本発明は以下の記載によっては限定されない。例１～１８は実施例であり、例１９～３９は比較例である。
［使用成分］
　本実施例および比較例で使用した成分を以下に示す。
（ポリウレタン樹脂（Ａ））
　ＨＤ－１０１３：
　商品名「ＨＤ－１０１３」（固形分６０質量％、ロックペイント社製）。ポリカーボネートポリオール（ａ１）である、３－メチル－１，５－ペンタンジオールを原料とするポリカーボネートジオールに、鎖伸長剤（ａ２）である１，６－ペンタンジオールと有機ジイソシアネート（ａ３）であるイソホロンジイソシアネート（ＩＰＤＩ）を反応させて得られるポリウレタン樹脂である。また、接着付与剤としてγ－グリシドキシプロピルトリエトキシシランが含有されている。
　Ａ－１１０２：
　商品名「タケラックＡ－１１０２」（固形分５０質量％、三井化学社製）。ポリカーボネートポリオール（ａ１）である、１，６－ヘキサンジオールを原料とするポリカーボネートジオールに、有機ジイソシアネート（ａ３）であるＩＰＤＩを反応させて得られるポリウレタン樹脂である。また、接着付与剤してγ－グリシドキシプロピルトリエトキシシランが含有されている。
（硬化剤（Ｂ））
　Ｈ－６２：
　商品名「Ｈ－６２」（イソシアネート含有量：１０質量％、固形分７５質量％、ロックペイント社製）。溶媒は酢酸エチルであり、主成分はＩＰＤＩとヘキサメチレンジイソシアネート（ＨＤＩ）のヌレート体である。
　Ａ－３０７０：
　商品名「タケネートＡ－３０７０」（イソシアネート含有量：１５質量％、固形分７５質量％、三井化学社製）。溶媒は酢酸エチルであり、主成分はＨＤＩのヌレート体である。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description. Examples 1 to 18 are examples, and examples 19 to 39 are comparative examples.
[Use ingredients]
The components used in the examples and comparative examples are shown below.
(Polyurethane resin (A))
HD-1013:
Trade name “HD-1013” (solid content 60 mass%, manufactured by Rock Paint). Polycarbonate polyol (a1), a polycarbonate diol using 3-methyl-1,5-pentanediol as a raw material, 1,6-pentanediol as a chain extender (a2), and isophorone diisocyanate as an organic diisocyanate (a3) It is a polyurethane resin obtained by reacting (IPDI). Further, γ-glycidoxypropyltriethoxysilane is contained as an adhesion promoter.
A-1102:
Trade name “Takelac A-1102” (solid content 50% by mass, manufactured by Mitsui Chemicals). This is a polyurethane resin obtained by reacting IPDI, which is an organic diisocyanate (a3), with polycarbonate diol, which is made from 1,6-hexanediol, which is a polycarbonate polyol (a1). Further, γ-glycidoxypropyltriethoxysilane is contained as an adhesion promoter.
(Curing agent (B))
H-62:
Product name “H-62” (isocyanate content: 10 mass%, solid content 75 mass%, manufactured by Rock Paint). The solvent is ethyl acetate, and the main component is a nurate of IPDI and hexamethylene diisocyanate (HDI).
A-3070:
Trade name “Takenate A-3070” (isocyanate content: 15 mass%, solid content 75 mass%, manufactured by Mitsui Chemicals, Inc.). The solvent is ethyl acetate, and the main component is HDI nurate.
（他の樹脂（Ｘ））
　ＮＴ－２５８：
　商品名「クリスボンＮＴ２５８」（固形分５０質量％、ＤＩＣ社製）。セバシン酸、イソフタル酸、ネオペンチルグリコールおよびイソホロンジイソシアネートを反応させたポリウレタン樹脂である。
　ＡＤ－７６Ｐ１：
　商品名「ＡＤ－７６Ｐ１」（東洋モートン社製）。スベリン酸、イソフタル酸、テレフタル酸およびエチレングリコールからなるポリエステル樹脂の末端をビスフェノールＡでエポキシ変性した固形分５５質量％のポリエステル樹脂である。
　Ａ－５１５：
　タケラックＡ－５１５（ポリエステルポリオール、固形分６０質量％、三井化学社製）。
（硬化剤（Ｙ））
　２０９６：
　商品名「コロネート２０９６」（日本ポリウレタン社製）。固形分９０質量％の脂肪族のヘキサメチレンジイソシアネートである。
　ＣＡＴ１０：
　商品名「ＣＡＴ１０」（東洋モートン社製）。固形分７５質量％の芳香族のトリレンジイソシアネートである。
　Ａ－５０：
　商品名「タケネートＡ－５０」（キシレンジイソシアネート、固形分７５質量％、三井化学社製）。 (Other resin (X))
NT-258:
Product name “Crisbon NT258” (solid content 50 mass%, manufactured by DIC Corporation). A polyurethane resin obtained by reacting sebacic acid, isophthalic acid, neopentyl glycol and isophorone diisocyanate.
AD-76P1:
Product name “AD-76P1” (manufactured by Toyo Morton). It is a polyester resin having a solid content of 55% by mass, in which the terminal of a polyester resin composed of suberic acid, isophthalic acid, terephthalic acid and ethylene glycol is epoxy-modified with bisphenol A.
A-515:
Takelac A-515 (polyester polyol, solid content 60 mass%, manufactured by Mitsui Chemicals).
(Curing agent (Y))
2096:
Product name “Coronate 2096” (manufactured by Nippon Polyurethane Co., Ltd.). It is an aliphatic hexamethylene diisocyanate having a solid content of 90% by mass.
CAT10:
Product name “CAT10” (manufactured by Toyo Morton). It is an aromatic tolylene diisocyanate having a solid content of 75% by mass.
A-50:
Product name “Takenate A-50” (xylene diisocyanate, solid content 75% by mass, manufactured by Mitsui Chemicals, Inc.).
（紫外線吸収剤（Ｃ））
　ＴＩＮＵＶＩＮ　４７９：
　商品名「ＴＩＮＵＶＩＮ　４７９」（ヒドロキシフェニルトリアジン系紫外線吸収剤、チバ・ジャパン社製）。
　ＴＩＮＵＶＩＮ　４７７：
　商品名「ＴＩＮＵＶＩＮ　４７７」（ヒドロキシフェニルトリアジン系紫外線吸収剤、チバ・ジャパン社製）。
（他の紫外線吸収剤（Ｚ））
　ＴＩＮＵＶＩＮ　ＰＳ：
　商品名「ＴＩＮＵＶＩＮ　ＰＳ」（ベンゾトリアゾール系紫外線吸収剤、チバ・ジャパン社製）。 (Ultraviolet absorber (C))
TINUVIN 479:
Product name “TINUVIN 479” (hydroxyphenyltriazine ultraviolet absorber, manufactured by Ciba Japan).
TINUVIN 477:
Product name “TINUVIN 477” (hydroxyphenyltriazine-based ultraviolet absorber, manufactured by Ciba Japan).
(Other UV absorbers (Z))
TINUVIN PS:
Product name “TINUVIN PS” (benzotriazole ultraviolet absorber, manufactured by Ciba Japan).
（光安定剤（Ｄ））
　ＨＡＬＳ　１２３：
　商品名「ＴＩＮＵＶＩＮ　１２３」（ヒンダードアミン系光安定剤、チバ・ジャパン社製）。 (Light stabilizer (D))
HALS 123:
Product name “TINUVIN 123” (hindered amine light stabilizer, manufactured by Ciba Japan).
［例１］
　主剤のポリウレタン樹脂（Ａ）であるＨＤ－１０１３の１００質量部（固形分）と、硬化剤（Ｂ）であるＨ－６２の１８．８質量部（固形分）と、紫外線吸収剤（Ｃ）であるＴＩＮＵＶＩＮ　４７９の７質量部と、光安定剤（Ｄ）であるＨＡＬＳ　１２３の１．５質量部とを混合して接着剤組成物を調製した。
　コロナ放電処理を施した厚さ２５μｍのＥＴＦＥフィルム（旭硝子社製、商品名：アフレックス）のコロナ放電処理面上に、アプリケータにて前記接着剤組成物を、乾燥後の塗布厚みが５μｍになるように塗工した。その後、乾燥機により７０℃で２分間乾燥し、相手材として前記と同様のコロナ放電処理を施した厚み２５μｍのＥＴＦＥフィルム（旭硝子社製、商品名：アフレックス）を、ニップ温度を７０℃に保持したラミネートロールにより圧着し、４０℃にて４８時間養生して積層体を得た。相手材のＥＴＦＥフィルムは、コロナ放電処理面を接着剤組成物と接する面とした。なお、それぞれのＥＴＦＥフィルムにおけるコロナ放電処理面は、表面濡れ指数を４０ｍＮ／ｍとした。該表面濡れ指数は、和光純薬社製の濡れ指数試薬を用いて、ＪＩＳ　Ｋ６７６８に準拠して測定した。
　得られた積層体を後述する耐候性の評価に用いた。 [Example 1]
100 parts by mass (solid content) of HD-1013 as the main polyurethane resin (A), 18.8 parts by mass (solid content) of H-62 as the curing agent (B), and UV absorber (C) 7 parts by mass of TINUVIN 479 and 1.5 parts by mass of HALS 123 as the light stabilizer (D) were mixed to prepare an adhesive composition.
On the corona discharge-treated surface of a 25 μm-thick ETFE film (trade name: Aflex, manufactured by Asahi Glass Co., Ltd.) subjected to corona discharge treatment, the adhesive composition is dried to a coating thickness of 5 μm with an applicator. Coated so that. Then, the ETFE film (trade name: Aflex, manufactured by Asahi Glass Co., Ltd.) having a thickness of 25 μm, which was dried with a dryer at 70 ° C. for 2 minutes and subjected to the same corona discharge treatment as described above, was brought to a nip temperature of 70 ° C. The laminated laminate was pressed and held at 40 ° C. for 48 hours to obtain a laminate. The ETFE film of the counterpart material had a corona discharge treated surface in contact with the adhesive composition. The corona discharge treatment surface of each ETFE film had a surface wetting index of 40 mN / m. The surface wetting index was measured according to JIS K6768 using a wetting index reagent manufactured by Wako Pure Chemical Industries.
The obtained laminate was used for evaluation of weather resistance described later.
［例２～３９］
　接着剤組成物の組成および塗布厚みと、接着剤組成物を塗布したＥＴＦＥフィルムに積層する相手材の種類を表１～３に示すように変更した以外は、例１と同様にして積層体を作製し、後述する耐候性の評価に用いた。
　ＥＴＦＥフィルム以外の相手材としては、厚み２５μｍのＰＥＴフィルムであるＴｅｉｊｉｎ　Ｐｏｌｙｅｓｔｅｒ　Ｆｉｌｍ　ＴＹＰＥ　Ｇ２Ｃ（コロナ処理品、帝人社製）を用い、コロナ放電処理面を接着剤組成物と接する面とした。 [Examples 2 to 39]
The laminate was prepared in the same manner as in Example 1 except that the composition and coating thickness of the adhesive composition and the type of the counterpart material laminated on the ETFE film coated with the adhesive composition were changed as shown in Tables 1 to 3. It produced and used for the weather resistance evaluation mentioned later.
As a counterpart material other than the ETFE film, Teijin Polyester Film TYPE G2C (corona-treated product, manufactured by Teijin Limited), which is a PET film having a thickness of 25 μm, was used, and the corona discharge-treated surface was a surface in contact with the adhesive composition.
［評価方法］
　各例で得られた積層体について、初期の波長３６０ｎｍの紫外線透過率、色差（イエローインデックス）および接着力と、以下に示す恒湿恒温試験後および促進耐候性試験後の波長３６０ｎｍの紫外線透過率、色差および接着力を測定し、評価を行った。
（恒温恒湿試験）
　得られた積層体に対して、温度８５℃×相対湿度８５％×１０００時間の恒温恒湿試験を実施した。 [Evaluation methods]
With respect to the laminate obtained in each example, the initial ultraviolet transmittance at a wavelength of 360 nm, the color difference (yellow index) and the adhesive strength, and the ultraviolet transmittance at a wavelength of 360 nm after the constant humidity and temperature test and the accelerated weather resistance test described below. The color difference and the adhesive strength were measured and evaluated.
(Constant temperature and humidity test)
A constant temperature and humidity test at a temperature of 85 ° C. and a relative humidity of 85% × 1000 hours was performed on the obtained laminate.
（促進耐候性試験（ＳＷＭ試験））
　得られた積層体に対して、促進耐候性試験機（スガ試験機社製、商品名：３００サンシャインウェザーメーター）を用い、ＪＩＳ　Ａ１４１５「高分子系建築材料の実験室光源による曝露試験方法」に準拠して暴露試験を行った。光源は、サンシャインカーボンアーク灯であり、放射照度を２５５Ｗ／ｍ２（３００－７００ｎｍ）、ＢＰＴ（ブラックパネル温度）を６３℃として運転し、４８分間の光照射と１２分間の光照射および降雨からなる合計６０分間のサイクルを１０００時間繰り返した。暴露形態としては、ＥＴＦＥフィルム面に光と水が当たるような暴露形態を採用した。 (Accelerated weather resistance test (SWM test))
For the obtained laminate, using an accelerated weathering tester (trade name: 300 Sunshine Weather Meter, manufactured by Suga Test Instruments Co., Ltd.), JIS A1415 “Exposure test method for polymer building materials with laboratory light sources” An exposure test was conducted in compliance. The light source is a sunshine carbon arc lamp, operated with an irradiance of 255 W / m 2 (300-700 nm), BPT (black panel temperature) of 63 ° C., and from 48 minutes of light irradiation, 12 minutes of light irradiation and rainfall The total 60 minute cycle was repeated for 1000 hours. As an exposure mode, an exposure mode in which light and water hit the ETFE film surface was adopted.
（紫外線透過率）
　各例の積層体について、島津製作所社製のＵＶ－３６００測定器を用いて波長３６０ｎｍの紫外線透過率（単位：％）を測定した。なお、積層体とする前の厚さ２５μｍの前記ＥＴＦＥフィルム単独の波長３６０ｎｍの紫外線透過率は９３％であり、厚さ２５μｍのＰＥＴフィルム単独の波長３６０ｎｍの紫外線透過率は８８％であった。積層体の紫外線透過率が低いほど、接着剤層の紫外線吸収性能が高いことを示す。波長３６０ｎｍ以下の紫外線透過率を２０％以内、より好ましくは１０％以内に抑えることができれば、ほとんどのプラスチックの光劣化を抑えることができる。 (UV transmittance)
The laminate of each example was measured for ultraviolet transmittance (unit:%) at a wavelength of 360 nm using a UV-3600 measuring instrument manufactured by Shimadzu Corporation. The ultraviolet transmittance at a wavelength of 360 nm of the ETFE film alone having a thickness of 25 μm before the laminate was 93%, and the ultraviolet transmittance at a wavelength of 360 nm of the PET film alone having a thickness of 25 μm was 88%. It shows that the ultraviolet-ray absorption performance of an adhesive bond layer is so high that the ultraviolet-ray transmittance of a laminated body is low. If the transmittance of ultraviolet rays having a wavelength of 360 nm or less can be suppressed to within 20%, more preferably within 10%, the light deterioration of most plastics can be suppressed.
（色差：イエローインデックス（△Ｙ・Ｉ））
　各例の積層体について、恒湿恒温試験および促進耐候性（ＳＷＭ）試験に基づく色差を、スガ試験機社製のＳＭ－Ｔカラーメーターを用い、ＪＩＳ　Ｚ８７２２に準処した透過測定方法でイエローインデックス（△Ｙ・Ｉ）を測定して評価した。△Ｙ・Ｉが小さいほど着色（黄変）が少ないことを示す。 (Color difference: Yellow index (△ Y ・ I))
For each of the laminates of the examples, the yellow index was measured by a transmission measurement method according to JIS Z8722 using a SM-T color meter manufactured by Suga Test Instruments Co., Ltd. for color difference based on a constant humidity and constant temperature test and an accelerated weather resistance (SWM) test. (ΔY · I) was measured and evaluated. It shows that there is so little coloring (yellowing) that (DELTA) Y * I is small.
（密着力）
　各例の積層体の密着力を、剥離強度（１８０度剥離、剥離速度５０ｃｍ／分）を測定して評価した（単位：Ｎ／ｃｍ）。 (Adhesion)
The adhesion of the laminates of each example was evaluated by measuring peel strength (180 degree peel, peel rate 50 cm / min) (unit: N / cm).
（総合評価）
　耐候性の総合評価は以下の基準で行った。
「○（良好）」：前記恒温恒湿試験および促進耐候性（ＳＷＭ）試験における１０００時間経過後に、密着力が３Ｎ／ｃｍ以上、△Ｙ・Ｉが１以下、波長３６０ｎｍの紫外線透過率の変化が１０％以下である。
「×（不良）」：前記恒温恒湿試験および促進耐候性（ＳＷＭ）試験における１０００時間経過後に、密着力が３Ｎ／ｃｍ以上、△Ｙ・Ｉが１以下、および波長３６０ｎｍの紫外線透過率の変化が１０％以下という条件のいずれか１つ以上が満たされていない。
　密着力が３Ｎ／ｃｍ以上、△Ｙ・Ｉが１以下であれば、密着力が維持された変色の少ない積層体であると評価できる。特に太陽電池のバックシートに関しては必須の評価項目である。また、積層体の色の変化だけでなく波長３６０ｎｍの紫外線透過率も評価対象とした。この試験においては、接着剤層やＰＥＴフィルムの湿熱劣化、および紫外線吸収剤の熱による揮散によって紫外線透過率が変化すると考えられる。
　各例の評価結果を表１～３に示す。なお、表１～３に示す接着剤組成物の各成分の配合量は固形分の質量（単位：質量部）である。また、促進耐候性試験後に「破壊」と評価したものは、ＰＥＴフィルムに亀裂が入って破壊が生じていたことを表す。 (Comprehensive evaluation)
The overall evaluation of weather resistance was performed according to the following criteria.
“Good (good)”: change in ultraviolet transmittance at a wavelength of 360 nm after adhesion of 3 N / cm or more, ΔY · I of 1 or less, after 1000 hours in the constant temperature and humidity test and accelerated weather resistance (SWM) test Is 10% or less.
“× (defect)”: After 1000 hours in the constant temperature and humidity test and accelerated weather resistance (SWM) test, the adhesion was 3 N / cm or more, ΔY · I was 1 or less, and the ultraviolet transmittance at a wavelength of 360 nm. Any one or more of the conditions where the change is 10% or less is not satisfied.
When the adhesion is 3 N / cm or more and ΔY · I is 1 or less, it can be evaluated that the adhesion is maintained and the laminate has little discoloration. In particular, it is an essential evaluation item for the back sheet of a solar cell. Moreover, not only the color change of a laminated body but the ultraviolet-ray transmittance of wavelength 360nm was also made into evaluation object. In this test, it is considered that the ultraviolet transmittance changes due to the wet heat deterioration of the adhesive layer and the PET film and the volatilization by the heat of the ultraviolet absorber.
The evaluation results of each example are shown in Tables 1 to 3. In addition, the compounding amount of each component of the adhesive composition shown in Tables 1 to 3 is the mass (unit: part by mass) of the solid content. Moreover, what was evaluated as “destructed” after the accelerated weather resistance test indicates that the PET film was cracked and was broken.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表１～３に示すように、本発明の接着剤組成物である例１～１８は、本発明の接着剤組成物以外の接着剤組成物である例１９～３９に比べて、促進耐候性試験と恒温恒湿試験において、いずれも１０００時間経過後の密着力、色差が良好であり、かつ、高い紫外線吸収能が維持されていた。また、相手材としてＥＴＦＥフィルムを用いた例１～３と、相手材としてＰＥＴフィルムを用いた例６～９では同様の結果が得られた。 As shown in Tables 1 to 3, Examples 1 to 18 which are the adhesive compositions of the present invention have accelerated weather resistance compared to Examples 19 to 39 which are adhesive compositions other than the adhesive composition of the present invention. In both the test and the constant temperature and humidity test, the adhesion and color difference after 1000 hours were both good, and the high ultraviolet absorption ability was maintained. Similar results were obtained in Examples 1 to 3 using an ETFE film as a counterpart material and Examples 6 to 9 using a PET film as a counterpart material.
　本発明の接着剤組成物により形成された接着剤層がフッ素樹脂フィルム等の樹脂フィルムからなる基材に積層された積層体は、高い密着力と優れた紫外線吸収機能を長期間に亘って持続でき、被着体の紫外線による劣化を防ぎ、各種印刷物や表示物の保護フィルム、太陽電池モジュールの表面材などへの利用が可能である。
　なお、２０１１年３月３日に出願された日本特許出願２０１１－０４６１８４号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The laminate in which the adhesive layer formed by the adhesive composition of the present invention is laminated on a substrate made of a resin film such as a fluororesin film, maintains a high adhesion and an excellent ultraviolet absorbing function over a long period of time. It is possible to prevent the adherend from being deteriorated by ultraviolet rays, and can be used for protective films for various printed materials and display materials, surface materials for solar cell modules, and the like.
It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-046184 filed on March 3, 2011 is cited here as the disclosure of the specification of the present invention. Incorporated.
　１　太陽電池モジュール
　１０、１０ａ、１０ｂ　積層体
　１１、１１ａ、１１ｂ　第１の基材
　１２、１２ａ、１２ｂ　接着剤層
　１３、１３ａ、１３ｂ　第２の基材
　２０　太陽電池セル
　３０ａ、３０ｂ　充填材 DESCRIPTION OF SYMBOLS 1 Solar cell module 10, 10a, 10b Laminated body 11, 11a, 11b 1st base material 12, 12a, 12b Adhesive layer 13, 13a, 13b 2nd base material 20 Solar cell 30a, 30b Filler

Claims (11)

  1. 　ポリカーボネートポリオール（ａ１）を原料とするポリウレタン樹脂（Ａ）と、硬化剤（Ｂ）と、トリアジン系紫外線吸収剤（Ｃ）と、光安定剤（Ｄ）とを含有する接着剤組成物。 An adhesive composition containing a polyurethane resin (A) using a polycarbonate polyol (a1) as a raw material, a curing agent (B), a triazine-based ultraviolet absorber (C), and a light stabilizer (D).
  2. 　前記硬化剤（Ｂ）が、イソシアヌレート体を含む、請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the curing agent (B) includes an isocyanurate body.
  3. 　前記トリアジン系紫外線吸収剤（Ｃ）がヒドロキシフェニルトリアジン系紫外線吸収剤を含む、請求項１または２に記載の接着剤組成物。 The adhesive composition according to claim 1 or 2, wherein the triazine-based ultraviolet absorber (C) contains a hydroxyphenyltriazine-based ultraviolet absorber.
  4. 　前記ヒドロキシフェニルトリアジン系紫外線吸収剤が、２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジンを含む、請求項３に記載の接着剤組成物。 The hydroxyphenyl triazine-based UV absorber is 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine. The adhesive composition according to claim 3, comprising:
  5. 　前記光安定剤（Ｄ）がヒンダードアミン系光安定剤を含む、請求項１～４のいずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, wherein the light stabilizer (D) comprises a hindered amine light stabilizer.
  6. 　前記ポリウレタン樹脂（Ａ）の水酸基と、前記硬化剤（Ｂ）のイソシアネート基との当量比ＮＣＯ／ＯＨが、１．０～５．０である、請求項１～５のいずれか一項に記載の接着剤組成物。 The equivalent ratio NCO / OH between the hydroxyl group of the polyurethane resin (A) and the isocyanate group of the curing agent (B) is 1.0 to 5.0, according to any one of claims 1 to 5. Adhesive composition.
  7. 　前記トリアジン系紫外線吸収剤（Ｃ）の含有量が、ポリウレタン樹脂（Ａ）の固形分１００質量部に対して、４～１１質量部である、請求項１～６のいずれか一項に記載の接着剤組成物。 The content of the triazine-based ultraviolet absorber (C) is 4 to 11 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin (A). Adhesive composition.
  8. 　前記光安定剤（Ｄ）の含有量が、ポリウレタン樹脂（Ａ）の固形分１００質量部に対して、０．２～５質量部である、請求項１～７のいずれか一項に記載の接着剤組成物。 The content of the light stabilizer (D) is 0.2 to 5 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin (A). Adhesive composition.
  9. 　フッ素樹脂フィルムからなる基材と、請求項１～８のいずれか一項に記載の接着剤組成物により前記基材上に形成された接着剤層とを有する積層体。 A laminate having a base material made of a fluororesin film and an adhesive layer formed on the base material by the adhesive composition according to any one of claims 1 to 8.
  10. 　前記フッ素樹脂フィルムが、エチレン－テトラフルオロエチレン系共重合体フィルムである、請求項９に記載の積層体。 The laminate according to claim 9, wherein the fluororesin film is an ethylene-tetrafluoroethylene copolymer film.
  11. 　請求項９または１０に記載の積層体を表面材および裏面材の少なくとも一方として有する太陽電池モジュール。 A solar cell module having the laminate according to claim 9 or 10 as at least one of a front surface material and a back surface material.
PCT/JP2012/055278 2011-03-03 2012-03-01 Adhesive composition, laminated body, and solar battery module WO2012118160A1 (en)

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US20140000702A1 (en) 2014-01-02
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TW201241127A (en) 2012-10-16
CN103380186A (en) 2013-10-30

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